Survey
* Your assessment is very important for improving the workof artificial intelligence, which forms the content of this project
Download XVIIth International Workshop on Quantum Atomic and Molecular
Document related concepts
Renormalization group wikipedia , lookup
Particle in a box wikipedia , lookup
Theoretical and experimental justification for the Schrödinger equation wikipedia , lookup
Quantum dot cellular automaton wikipedia , lookup
Quantum computing wikipedia , lookup
Bell's theorem wikipedia , lookup
Interpretations of quantum mechanics wikipedia , lookup
Molecular Hamiltonian wikipedia , lookup
Quantum teleportation wikipedia , lookup
EPR paradox wikipedia , lookup
Quantum machine learning wikipedia , lookup
Symmetry in quantum mechanics wikipedia , lookup
Quantum group wikipedia , lookup
History of quantum field theory wikipedia , lookup
Canonical quantization wikipedia , lookup
Quantum key distribution wikipedia , lookup
Franck–Condon principle wikipedia , lookup
Quantum state wikipedia , lookup
Hidden variable theory wikipedia , lookup
Atomic theory wikipedia , lookup
Two-dimensional nuclear magnetic resonance spectroscopy wikipedia , lookup
Transcript
XVIIth International Workshop on Quantum Atomic and Molecular Tunneling in Solids and other Phases Hotel Dorint – Blüemlisalp, Beatenberg/Interlaken, Switzerland May 31 – June 3, 2015 Executive Committee Jürgen Eckert Frédéric Merkt Beat H. Meier Martin Quack Local Committee Ruth Schüpbach, Georg Seyfang, Sieghard Albert, Irina Bolotova, Ziqiu Chen, Csaba Fábri, Ľuboš Horný and Urs Hollenstein, ETH Zürich The organizing committee would like to thank Swiss Chemical Society Division of Fundamental Research swiss-chem-soc.ch Deutsche Bunsen-Gesellschaft für Physikalische Chemie www.bunsen.de Contact Group for Research Matters BASF SE www.basf.com F. Hoffmann-La Roche Ltd. www.roche.com Syngenta International AG www.syngenta.com Novartis AG www.novartis.com © 2015 with the editors J. Eckert, B. Meier, F. Merkt, and M. Quack Proceedings of ‘Quantum Atomic and Molecular Tunneling in Solids and other Phases’, Beatenberg/Interlaken, 2015 Dear Friends, Speakers, Participants, Enjoy the science of tunneling and the landscape at QAMTS 2015 in Beatenberg Switzerland! This is the 17th edition of a highly successful series of international workshops on the topic of Quantum Atomic and Molecular Tunneling in Solids and other Phases, the previous one having taken place in Santa Fe, New Mexico, USA in 2012 (see also QAMTS history). The tunnel effect has been a crucial quantum phenomenon starting in the early days of quantum mechanics with the theoretical work of Friedrich Hund (1926/27) on quantum effects in molecular isomerization reactions and George Gamow (1928) on the theory of radioactive alpha decay, both being connected to ‘heavy’ particle motion (of the corresponding He nuclei or ‘atoms and molecules’) and thus fitting into the framework of the QAMTS workshops. Since then, numerous phenomena related to this effect, completely absent, even unthinkable of in classical mechanics have been discovered and continue to be discovered at a regular rate, with also many applications in chemistry and molecular physics. We look forward to learning about some of the most recent and exciting developments in this field. Slight changes have been applied to the preliminary program time table, but the speakers and chairmen concerned were contacted individually. The large majority of the other times and duties remain unchanged. Please check for your times and duties. Note that the free informal discussion afternoon with possible excursions can be either on Wednesday or on Tuesday depending on weather conditions. The lecture program for these afternoons will be exchanged accordingly. Thus speakers planned for Wednesday afternoon should be also prepared to give their talks on Tuesday afternoon instead of Wednesday. The decision on this will be taken on Monday afternoon at the latest, depending on weather forecast. Posters will remain mounted during the whole meeting. Remember the unique nature of this series of workshops. As in the past, the hallmark of QAMTS is the highly cross disciplinary nature, which includes work on tunneling of protons and heavier species in condensed or any other phases and in chemical reactions, transport in condensed phases, rotational tunneling, biological systems, studied by experiment or by theory. Lecture times (40 minutes or 20 minutes) include discussion times and it is customary to leave enough time for discussion. We thank the Swiss Chemical Society, the Contact group for Research Matters (KGF Basel; BASF SE, F. Hoffmann-La Roche Ltd., Syngenta International AG, Novartis AG) and the Bunsen-Society for Physical Chemistry as well as the Royal Society of Chemistry with PCCP and Taylor and Francis with Molecular Physics for sponsorship and support. Zurich, May 2015 The Executive Committee: Jürgen Eckert, University of South Florida Beat H. Meier, Frédéric Merkt, and Martin Quack, ETH Zurich Local Committee: Ruth Schüpbach, Georg Seyfang, Sieghard Albert, Irina Bolotova, Ziqiu Chen, Csaba Fábri, Ľuboš Horný and Urs Hollenstein ETH Zurich History of QAMTS Workshops XVII QAMTS 2015 International Workshop on Quantum Atomic and Molecular Tunneling in Solids and other Phases Beatenberg/Interlaken, Switzerland 31.5.–3.6.2015 Jürgen Eckert, Beat H. Meier, Frédéric Merkt, and Martin Quack http://qamts.ethz.ch/qamts2015/ XVI QAMTS 2012 International Workshop on Quantum Atomic and Molecular Tunneling in Solids and other Condensed Phases Santa Fe 10.6.–14.6.2012 Juergen Eckert, Bill Poirier http://www.myweb.ttu.edu/lpoirier/QAMTS/Program.html XV QAMTS 2010 International Workshop on Quantum Atomic and Molecular Tunneling in Solids and other Condensed Phases Technical University Darmstadt, Germany 5.9.–9.9.2010 Gerd Buntkowsky, Juergen Eckert http://cgi.chemie.tu-darmstadt.de/QAMTS2010/Getting_There.html XIV QAMTS 2007 International Workshop on Quantum Atomic and Molecular Tunneling in Solids and other Condensed Systems University of Houston, USA, 28.10.–11.11.2007. XIII QAMTS 2005 International Workshop on Quantum Atomic and Molecular Tunneling in Solids and other Condensed Phases Antonio Fernández-Ramos, Zorka Smedarchina University of Santiago del Compostela, Spain, 27.7.–31.7.2005 XII XI X QAMTS 2003 International Workshop on Atomic and Molecular Tunneling in Solids University of Florida, Gainesville, USA 22.6.–25.6.2003 QAMTS 2001 Quantum Atom and Molecular Tunneling in Solids University of Nottingham, United Kingdom 5.9.–9.9.2001 A. J. Horsewill http://www.nottingham.ac.uk/~ppzajh/qamts/index.html QAMTS 1999 Quantum Atomic and Molecular Tunnelling in Solids Zdzislaw Lalowicz, Zbigniew Olejniczak University of Krakov, Poland, 26.–30.9.1999 IX VIII VII VI V QAMTS 1997 Quantum Tunnelling of Atoms and Molecules in Solids Forschungszentrum Jülich, Germany QAMTS 1995 Quantum Tunnelling of Atoms and Molecules in Solids F. Fillaux, H. G. Büttner, G.J. Kearly, J. Meinnel Institut Laue-Langevin, Château de la Baume, Seyssins/Grenoble 4.10.–7.10.1995 Proceedings: Physica B: Condensed Matter Vol. 226, no. 1/3 http://www.sciencedirect.com/science/journal/09214526/226/1-3 QAMTS 1993 Quantum Molecular Tunnelling in Solids Cumberland Lodge, Windsor (UK) 12.7.–15.7.1993 C. J. Carlile, A. J. Horsewill Proceedings: Physica B: Condensed Matter Vol. 202, no. 3/4 (1994) http://www.sciencedirect.com/science/article/pii/0921452694902941# QAMTS 1991 Castle Ringberg, Tegernsee, Germany QAMTS 1988 Turku, Finnland IV QAMTS 1986 Quantum Aspects of Molecular Motions in Solids Grenoble, France, 24.–26.9. 1986 A. Heidemann, A. Magerl, D. Richter, M. Prager, T. Springer Proceedings: Springer Proceedings in Physics, Volume 17, 1987 http://link.springer.com/book/10.1007/978-3-642-71914-1 III QAMTS 1984 University of Nottingham, United Kingdom II I QAMTS 1982 Braunschweig, Germany QAMTS 1981 Institut für Festkörperforschung, Kernforschungsanlage Jülich, Germany The scope has widened over the years, and in the future one may wish to maintain the QAMTS acronym with the new and now more appropriate interpretation: ‘Quantum Atomic and Molecular Tunneling Systems’ XVIIth International Workshop on Quantum Atomic and Molecular Tunneling in Solids and other Phases Hotel Dorint – Blüemlisalp, Beatenberg/Interlaken, Switzerland http://qamts.ethz.ch/qamts2015/ , http://hotel-interlaken.dorint.com/ Sunday 31 May through Wednesday 3 June 2015 Sunday, 31 May 2015 Session 1, Chairman Martin Quack after 09:30 Welcome coffee and registration 10:15 – 10:30 Martin Quack Welcome and Introduction 10:30 – 11:10 Takamasa Momose (PCCP Lecturer) Tunneling Reaction of Methyl Radicals with Molecular Hydrogen 11:10 – 11:50 Bruce C. Garrett Tunneling in Gas-Phase Reactions of H Isotopes with H2 11:50 – 12:30 Zlatko Bačić Small Molecules in Nanoscale Cavities: Quantum Dynamics, Inelastic Neutron Scattering Spectra and New Selection Rules 12:30 – 14:00 Lunch Session 2, Chairman Jürgen Eckert 14:00 – 14:40 Alexander I. Kolesnikov Quantum tunneling of ultra-confined water 14:40 – 15:20 Attila G. Császár Tunneling phenomena in simple molecular systems 15:20 – 16:00 Jochen Küpper Quantum molecular tunneling in external electric and laser fields 16:00 – 16:30 Coffee Break Session 3, Chairman Beat H. Meier 16:30 – 17:10 Jacek Waluk Double hydrogen tunnelling in porphycenes: from condensed phases to isolated and single molecules 17:10 – 17:50 Wolfram Sander Tunneling in Intermolecular Carbene Reactions 17:50 – 18:30 Jean-Michel Mestdagh Dynamics of Intramolecular Hydrogen Transfer Reactions in Small Organic Molecules 18:30 – 19:10 Bruce L. Yoder Barrierless proton transfer across weak CH···O hydrogen bonds in dimethyl ether dimer 19:10 – 19:30 Sebastian Kozuch A Theoretical Approach to Heavy Atom Tunneling: The Physical Limits for Reactivity and Selectivity 19:30 – 21:00 Dinner Posters and Discussion 21:00 Monday, 1 June 2015 Session 4, Chairman Frédéric Merkt 08:30 – 09:10 Hans-Heinrich Limbach Bio-inspired NMR Studies of Hydrogen Transfer and Bonding 09:10 – 09:50 Beat H. Meier The Haupt effect in solid state NMR 09:50 – 10:30 Bill Poirier Exact Quantum Dynamical Treatment of Hydrogen-material Interactions 10:30 – 11:00 Coffee Break Session 5, Chairman Attila G. Császár 11:00 – 11:40 Pavel L. Chapovsky Tunneling of open quantum systems: Nuclear spin isomers of molecules 11:40 – 12:20 Samuel Leutwyler Competing Excitonic Energy Transfer and Double Proton Transfer in the 7-Azaindole Dimer 12:30 – 14:00 Lunch Session 6, Chairman Bill Poirier 14:00 – 14:40 Roberto Marquardt Diffusion Dynamics of Adsorbates: New Insight on Tunneling and Other Quantum Effects from an Old Formula 14:40 – 15:20 Wolfgang Jäger Tunneling Effects in Rotational Spectra of Water-Containing Complexes 15:20 – 16:00 Malcolm H. Levitt Spin Isomers and Long-lived States: The crossover point from quantum rotors to room-temperature NMR 16:00 – 16:30 Coffee Break Session 7, Chairman Roberto Marquardt 16:30 – 17:10 Sieghard Albert Tunneling dynamics studied by high resolution FTIR/ THz spectroscopy with and without synchrotron light 17:10 – 17:50 François Dulieu Atomic O diffusion on amorphous surfaces between 7 and 70 K: at what temperature does quantum tunneling dominate? 17:50 – 18:30 Pierre Asselin Jet-cooled high resolution infrared spectroscopy of molecular complexes 18:30 – 19:10 Katrin Dulitz Tunneling in molecules probed by high resolution photoelectron spectroscopy 19:10 – 19:30 Ľuboš Horný Computation of Molecular Parity Violation in View of Spectroscopic Experiments 19:30 – 21:00 Dinner Posters and Discussions 21:00 Tuesday, 2 June 2015 Session 8, Chairman Samuel Leutwyler 08:30 – 09:10 Rudolf K. Allemann Dynamic Effects in Enzyme Catalysis 09:10 – 09:50 Jiří Vaníček Accelerating quantum instanton calculations of kinetic isotope effects on tunneling rates 09:50 – 10:30 Amnon Kohen Kinetic Isotope Effects as Probe for Hydrogen Tunneling in Enzymes 10:30 – 11:00 Coffee Break Session 9, Chairman Wolfram Sander 11:00 – 11:40 Weston Thatcher Borden Tunnelling in the Degenerate Rearrangement of Semibullvalene at Cryogenic Temperatures – An Experimental Test of a Theoretical Prediction 11:40 – 12:20 Jörn Manz Concerted Electronic and Nuclear Fluxes During Coherent Tunneling 12:30 – 14:00 – 19:30 – Lunch Afternoon free discussion, Posters, excursions. In case of bad weather the Tuesday afternoon will have the program planned for Wednesday, and Wednesday afternoon will accordingly be free for informal discussions and excursions. Decision on this will be on Monday. 21:00 Dinner Posters and Discussions 21:00 Wednesday, 3 June 2015 Session 10, Chairman Hans Limbach 08:30 – 09:10 David J. Wales Energy Landscapes: Prediction of Molecular Properties 09:10 – 09:50 Michele Parrinello Path Integral Metadynamics 09:50 – 10:30 Jürgen Eckert Potential Energy Surfaces for Hydrogen in Porous Materials Probed by Rotational Tunneling Spectroscopy 10:30 – 11:00 Coffee Break Session 11, Chairman Jiří Vaníček 11:00 – 11:40 Maciej Krzystyniak Mass selective neutron spectroscopy 11:40 – 12:20 Georg Ch. Mellau The connection between the internal dynamics below and above the isomerization barrier for the [H,C,N] molecular system 12:20 – 14:00 Lunch Session 12, Chairman Weston Thatcher Borden 14:00 – 14:40 Wolfgang E. Ernst Molecular Dynamics and Cluster Formation in Cold Helium Droplets 14:40 – 15:20 Hans Jakob Wörner High-harmonic spectroscopy of attosecond quantum dynamics 15:20 – 16:00 Vincenzo Aquilanti Benchmarking reaction kinetics astride the transition between the moderate and deep tunnelling regimes 16:00 – 16:30 Coffee Break Session 13, Chairman Amnon Kohen 16:30 – 17:10 Robert J. McMahon Quantum Mechanical Tunneling Reactions of Organic Reactive Intermediates 17:10 – 17:50 Jernej Stare Multiscale computational enzymology: Empirical Valence Bond simulation of benzylamine degradation catalysed by monoamine oxidase 17:50 – 18:30 Johannes Kästner Quantum Mechanical Tunneling of Atoms in Water, Biochemistry and Astrochemistry 18:30 – 18:50 Georg Seyfang Ultrahigh resolution measurements of ro-vibrational-tunneling transitions in NH3: absolute frequencies and quadrupole splittings 18:50 – 19:10 Csaba Fábri Full-Dimensional Quantum Dynamics and Spectroscopy of Ammonia Isotopomers 19:10 – 19:30 Igor Reva Generation of Higher-Energy Conformers and Proton Tunneling in Matrix-Isolated Molecules Containing OH group 20:00 Thursday, 4 June 2015 Departure after Breakfast Conference Dinner Contents PCCP Lecture Tunneling Reaction of Methyl Radicals with Molecular Hydrogen Takamasa Momose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Lectures Tunneling in Gas-Phase Reactions of H Isotopes with H2 Bruce C. Garrett, Donald G. Truhlar, Steven L. Mielke, and Donald G. Fleming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . SMALL MOLECULES IN NANOSCALE CAVITIES: QUANTUM DYNAMICS, INELASTIC NEUTRON SCATTERING SPECTRA, AND NEW SELECTION RULES Zlatko Bačić . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Quantum tunneling of ultra-confined water A.I. Kolesnikov, L.M. Anovitz, G. Ehlers, E. Mamontov, A. Podlesnyak, T.R. Prisk, A. Seel, and G.F. Reiter . . . . . . . . . . . . . . . . . . . . . Tunneling phenomena in simple molecular systems Attila G. Császár, Peter R. Schreiner, and Wesley D. Allen . . . . . . . . Quantum molecular tunneling in external electric and laser fields Jochen Küpper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Double hydrogen tunnelling in porphycenes: from condensed phases to isolated and single molecules Jacek Waluk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tunneling in Intermolecular Carbene Reactions Stefan Henkel, Melanie Ertelt, Paolo Costa, Iris Trosien, Wolfram Sander Dynamics of Intramolecular Hydrogen Transfer Reactions in Small Organic Molecules J.-M Mestdagh, C. Crépin, M. Chevalier, A. Gutierrez-Quintanilla, M. Briant, L. Poisson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Barrierless proton transfer across weak CH· · · O hydrogen bonds in dimethyl ether dimer Bruce L. Yoder, Ksenia B. Bravaya, Andras Bodi, and Ruth Signorell . . A Theoretical Approach to Heavy Atom Tunneling: The Physical Limits for Reactivity and Selectivity Sebastian Kozuch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Bio-inspired NMR Studies of Hydrogen Transfer and Bonding Hans-Heinrich Limbach . . . . . . . . . . . . . . . . . . . . . . . . . . . . i L-1 L-2 L-3 L-4 L-5 L-6 L-7 L-8 L-9 L-10 L-11 L-12 Contents The Haupt Effect in Solid-State NMR Beat H. Meier, Fabian Jähnig, Michael Batel, Marco Tomaselli, Anders B. Nielsen, and Matthias Ernst . . . . . . . . . . . . . . . . . . . . . . . Exact Quantum Dynamical Treatment of Hydrogen-material Interactions Jason McAfee, Megan Gonzalez, Adelia Aquino, and Bill Poirier . . . . . Tunneling of open quantum systems: Nuclear spin isomers of molecules P.L. Chapovsky . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Competing Excitonic Energy Transfer and Double Proton Transfer in the 7-Azaindole Dimer Philipp Ottiger, Zhifeng Xue and Samuel Leutwyler . . . . . . . . . . . . Diffusion Dynamics of Adsorbates: New Insight on Tunneling and Other Quantum Effects from an Old Formula Thiago Firmino, Roberto Marquardt, Fabien Gatti, and Wei Dong . . . . Tunneling Effects in Rotational Spectra of Water-Containing Complexes Elijah G. Schnitzler, Brandi L. M. Zenchyzen, Supriya Ghosh, Javix Thomas, Yunjie Xu, and Wolfgang Jäger . . . . . . . . . . . . . . . . . . Spin Isomers and Long-lived States: The crossover point from quantum rotors to room-temperature NMR Malcolm H. Levitt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tunneling dynamics studied by high resolution FTIR/ THz spectroscopy with and without synchrotron light Sieghard Albert, Ziqiu Chen, Philippe Lerch and Martin Quack . . . . . Atomic O diffusion on amorphous surfaces between 7 and 70 K: at what temperature does quantum tunneling dominate? Francois Dulieu, Marco Minissale, Emanuele Congiu, Henda Chaabouni and Saoud Baouche . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Jet-cooled high resolution infrared spectroscopy of molecular complexes P. Asselin, Y. Berger, P. Soulard, M. Goubet, T. R. Huet, R. Georges, O. Pirali . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tunneling in molecules probed by high-resolution photoelectron spectroscopy Katrin Dulitz, Urs Hollenstein, Konstantina Vasilatou, and Frédéric Merkt Computation of Molecular Parity Violation in View of Spectroscopic Experiments Ľuboš Horný and Martin Quack . . . . . . . . . . . . . . . . . . . . . . . Dynamic Effects in Enzyme Catalysis Louis Y. P. Luk, E. Joel Loveridge, Rudolf K. Allemann . . . . . . . . . Accelerating quantum instanton calculations of kinetic isotope effects on tunneling rates Konstantin Karandashev and Jiří Vaníček . . . . . . . . . . . . . . . . . ii L-13 L-14 L-15 L-16 L-17 L-18 L-19 L-20 L-21 L-22 L-23 L-24 L-25 L-26 iii Contents Kinetic Isotope Effects as Probe for Hydrogen Tunneling in Enzymes Amnon Kohen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tunnelling in the Degenerate Rearrangement of Semibullvalene at Cryogenic Temperatures – An Experimental Test of a Theoretical Prediction Melanie Ertelt, Stefan Henkel, Wolfram Sander, Xue Zhang, David A. Hrovat, and Weston Thatcher Borden . . . . . . . . . . . . . . . . . . . Concerted Electronic and Nuclear Fluxes During Coherent Tunneling Timm Bredtmann, Si-Dian Li, Jörn Manz, Wen-Juan Tian, Yan-Bo Wu, Yonggang Yang, and Hua-Jin Zhai . . . . . . . . . . . . . . . . . . . . Energy Landscapes: Prediction of Molecular Properties David J. Wales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Path Integral Metadynamics Michele Parrinello . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Potential Energy Surfaces for Hydrogen in Porous Materials Probed by Rotational Tunneling Spectroscopy Tony Pham and Juergen Eckert . . . . . . . . . . . . . . . . . . . . . . Mass selective neutron spectroscopy M. Krzystyniak . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The connection between the internal dynamics below and above the isomerization barrier for the [H,C,N] molecular system Georg Ch. Mellau, Alexandra A. Kyuberis, Oleg L. Polyansky, Nikolai Zobov, and Robert W. Field . . . . . . . . . . . . . . . . . . . . . . . . Molecular Dynamics and Cluster Formation in Cold Helium Droplets Wolfgang E. Ernst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . High-harmonic spectroscopy of attosecond quantum dynamics P. M. Kraus, D. Baykusheva, Ch. Roth, L. Horny and H. J. Wörner . . Benchmarking reaction kinetics astride the transition between the moderate and deep tunnelling regimes Simonetta Cavalli, Dario De Fazio, and Vincenzo Aquilanti . . . . . . . Quantum Mechanical Tunneling Reactions of Organic Reactive Intermediates Hiroshi Inui and Robert J. McMahon . . . . . . . . . . . . . . . . . . . Multiscale computational enzymology: Empirical Valence Bond simulation of benzylamine degradation catalyzed by monoamine oxidase Jernej Stare . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Quantum Mechanical Tunneling of Atoms in Water, Biochemistry and Astrochemistry T.P.M (Fedor) Goumans, Sonia Álvarez-Barcia, Judith B. Rommel, and Johannes Kästner . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . L-27 . L-28 . L-29 . L-30 . L-31 . L-32 . L-33 . L-34 . L-35 . L-36 . L-37 . L-38 . L-39 . L-40 Contents iv Ultrahigh resolution measurements of ro-vibrational- tunneling transitions in NH3 : absolute frequencies and quadrupole splittings Peter Dietiker, Eduard Milogyadov, Martin Quack, Andreas Schneider, Georg Seyfang . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . L-41 Full-Dimensional Quantum Dynamics and Spectroscopy of Ammonia Isotopomers Csaba Fábri, Roberto Marquardt, and Martin Quack . . . . . . . . . . . L-42 Generation of Higher-Energy Conformers and Proton Tunneling in Matrix-Isolated Molecules Containing OH group Igor Reva . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . L-43 Poster contributions MOGADOC Database Update: Diversity of Molecular Structures with Large-Amplitude Motion, Tunnelling and Other Effects Natalja Vogt, Rainer Rudert, and Jürgen Vogt . . . . . . . . . . . . . . . P-1 Quantum Tunneling in the Hydrogenation of Singlet and Triplet Carbenes Probed by Matrix Isolation Spectroscopy Stefan Henkel and Wolfram Sander . . . . . . . . . . . . . . . . . . . . . P-2 Valence-shell-photoelectron imaging of complex molecules Joss Wiese, Sebastian H. Trippel, and Jochen Küpper . . . . . . . . . . . P-3 Tunneling as a Source of Hyperpolarization in Nuclear Magnetic Resonance F. Jähnig, A. B. Nielsen, B. H. Meier, and M. Ernst . . . . . . . . . . . . P-4 Modulation Techniques in Vacuum-Ultraviolet High-Resolution Absorption Spectroscopy U. Hollenstein, H. Schmutz, and F. Merkt . . . . . . . . . . . . . . . . . P-5 Tunneling and Parity Violation in Trisulfane (HSSSH): An Almost Ideal Molecule for Detecting Parity Violation in Chiral Molecules Csaba Fábri, Ľuboš Horný, and Martin Quack . . . . . . . . . . . . . . . P-6 High Resolution Analysis of the FTIR spectra and quantum dynamics of CHF3 : The 2ν4 (A1 /E) Band Irina Bolotova, Oleg Ulenikov, Elena Bekhtereva, Sieghard Albert, Hans Hollenstein, and Martin Quack . . . . . . . . . . . . . . . . . . . . . . . P-7 A combined submm wave and synchrotron-based Fourier transform infrared spectroscopic study of meta- and ortho-D-phenol: Probing tunneling switching dynamics Ziqiu Chen, Sieghard Albert, Robert Prentner, and Martin Quack . . . . P-8 Study of large amplitude motions by photoelectron spectroscopy in ethane and 2-butyne radical cations U. Jacovella, C. Lauzin, B. Gans, M. Grütter and F. Merkt . . . . . . . . P-9 Contents High resolution infrared spectroscopy and theory of parity violation and tunneling for dithiine as a candidate for measuring the parity violating energy difference between enantiomers of chiral molecules S. Albert, I. Bolotova, Z. Chen, C. Fabri, L. Horny, M. Quack, G. Seyfang and D. Zindel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v P-10 L-1 QAMTS 2015 – PCCP Lecture PCCP Lecture Tunneling Reaction of Methyl Radicals with Molecular Hydrogen Takamasa Momose Department of Chemistry, The University of British Columbia, 2036 Main Mall, Vancouver BC, V6T 1Z1, CANADA The tunneling effect becomes important in chemical reactions at low temperature because of the suppression of thermally activated reaction processes. Such a situation is expected to be realized in reactions in interstellar clouds, for example. However, direct measurements of tunneling rate constants in laboratories is difficult due to the interference of co-existing thermal reactions. Solid parahydrogen is a unique environment for the study of chemical reactions of molecules at liquid helium temperatures because of the softness of the solid as a quantum crystal [1]. In previous studies, we reported that methyl radicals produced in parahydrogen crystals react with a neighboring hydrogen molecule to form methane even at 4 K [2, 3]. Since the barrier of the reaction is estimated to be about 11 kcal mol−1 (∼ 5000 K), the occurrence of the reaction at 4 K must be ascribed exclusively to pure tunneling. From the temporal changes in the intensity of vibrational transitions of the methyl radicals and methane molecules, the tunneling reaction rate for the reaction of CD3 + H2 → CD3 H + H in solid parahydrogen is determined to be 3.3×10−6 s−1 , while no tunneling reaction occurred in a CH3 + H2 system. It was also found that the tunneling reaction rates change upon irradiation from the light source of the FTIR spectrometer [4]. We will discuss the nature of the tunneling chemical reactions between a methyl radical and a hydrogen molecule based on our experimental data. [1] T. Momose, and T. Shida, Bull. Chem. Soc. Jpn, 71, 1 (1998). [2] T. Momose, H. Hoshina, N. Sogoshi, H. Katsuki, T. Wakabayashi, and T. Shida, J. Chem. Phys. 108, 7334 (1998). [3] H. Hoshina, M. Fushitani, T. Momose and T. Shida, J. Chem. Phys. 120, 3706 (2004). [4] C. Toh, P. Djuricanin, and T. Momose, to be submitted. L-2 QAMTS 2015 – Lectures Tunneling in Gas-Phase Reactions of H Isotopes with H2 Bruce C. Garrett,1 Donald G. Truhlar, 2 Steven L. Mielke,2 and Donald G. Fleming3 1 Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, USA 2 Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, MN, USA 3 Department of Chemistry, University of British Columbia, Vancouver, BC, Canada The reactions of atomic hydrogen and its isotopes with molecular hydrogen are the prototype testing ground for reaction rate theories. A clear conclusion from early work was that quantum mechanical effects on nuclear motion, especially tunneling and zero-point energies, play a significant role in these reactions. More recently, theoretical and experimental studies of the reaction of muonium (Mu, a pseudo isotope of protium consisting of a positive muon orbited by an electron and having a mass of 0.114 amu) have provided a unique opportunity to learn more about the quantal effects on this chemical reaction. Accurate quantum mechanical results on the Mu + H2 reaction provided a stringent test of approximate approaches that allowed interpretations of the features controlling reactions. This presentation will review recent experimental and theoretical studies [1-4] on reactions of H isotopes with H2 that illustrate the importance of quantum mechanical tunneling and clearly demonstrate the validity of the vibrational adiabatic model (see Figure 1). For example, in both collinear and 3D quantal calculations, the energy where the accurate reaction probability equals 0.5, which can be interpreted as the quasiclassical dynamical threshold energy, is in good agreement with the ground-state vibrationally adiabatic barrier energy. Figure 1. The good agreement between the adiabatic model (solid blue curve) and accurate quantum mechanics (long dash green curve) for Mu+H2 reaction probabilities with zero total angular momentum demonstrates the validity of the adiabatic model. This result contradicts the interpretation of Aoiz and coworkers [5] that the collinear adiabatic potential (short dashed red curve) should be used to describe tunneling for the 3D reaction. [1] S. L. Mielke, B. C. Garrett, D. G. Fleming, and D. G. Truhlar, Molecular Physics 113 (2), 160 (2015). [2] P. Bakule, D. G. Fleming, O. Sukhorukov, K. Ishida, F. Pratt, T. Momose, E. Torikai, S. L. Mielke, B. C. Garrett, K. A. Peterson, G. C. Schatz, and D. G. Truhlar, Journal of Physical Chemistry Letters 3 (19), 2755 (2012). [3] D. G. Fleming, D. J. Arseneau, O. Sukhorukov, J. H. Brewer, S. L. Mielke, D. G. Truhlar, G. C. Schatz, B. C. Garrett, and K. A. Peterson, J. Chem. Phys. 135 (18), 184310 (2011). [4] D. G. Fleming, D. J. Arseneau, O. Sukhorukov, J. H. Brewer, S. L. Mielke, G. C. Schatz, B. C. Garrett, K. A. Peterson, and D. G. Truhlar, Science 331 (6016), 448 (2011). [5] J. Aldegunde, P. G. Jambrina, E. Garcia, V. J. Herrero, V. Saez-Rabanos, and F. J. Aoiz, Molecular Physics 111 (21), 3169 (2013). L-3 QAMTS 2015 – Lectures Contribution to the QAMTS Workshop 2015 Zlatko Bačić Department of Chemistry, New York University, New York, NY 10003, USA SMALL MOLECULES IN NANOSCALE CAVITIES: QUANTUM DYNAMICS, INELASTIC NEUTRON SCATTERING SPECTRA, AND NEW SELECTION RULES The behavior of small hydrogen-containing molecules (H2, HF, H2O, CH4) inside nanoscale cavities of diverse host materials, e.g., fullerenes, carbon nanotubes, clathrate hydrates, and metal-organic frameworks, has received a great deal of attention in recent years. In nanoscale confinement, the translational center-of-mass motions of the caged molecules are quantized and strongly coupled to the molecular rotations, which are also quantized. I will review our rigorous quantum treatment of the intricate coupled translation-rotation (TR) dynamics of the caged diatomic (H2/HD/D2) and polyatomic (CH4) molecules in 5D and 6D, respectively. These calculations have revealed distinct spectroscopic signatures of the TR coupling, which were later observed in the infrared and Raman spectra recorded for H2 in C60 and C70. The TR eigenstates can be probed directly and with high selectivity by the inelastic neutron scattering (INS) spectroscopy. This has motivated our recent development of the methodology for accurate quantum simulations of the INS spectra of a hydrogen molecule in a nanocavity of an arbitrary shape, which incorporates the coupled TR wave functions from the 5D bound-state calculations [1]. The INS spectra of H2 and isotopologues inside the cages of C60 and clathrate hydrates, and their temperature dependence, computed using this methodology have allowed us to interpret and assign the INS spectra measured for these systems for a range of temperatures [2]. This work has led to the formulation of the new and unexpected selection rule for the INS spectroscopy of H2/HD in a near-spherical nanocavity, the first ever to be established in the INS of discrete molecular compounds [2]. In our recent INS study of H2/HD confined inside C60, the transitions predicted to be forbidden by the selection rule were found to be systematically absent from the measured INS spectra, thus confirming its validity [3]. [1] M. Xu, L. Ulivi, M. Celli, D. Colognesi, and Z. Bačić, Phys. Rev. B 83, 241403(R) (2011). [2] M. Xu, S. Ye, A. Powers, R. Lawler, N. J. Turro, and Z. Bačić, J. Chem. Phys. 139, 064309 (2013). [3] M. Xu, M. Jiménez-Ruiz, M. R. Johnson, S. Rols, S. Ye, M. Carravetta, M. S. Denning, X. Lei, Z. Bačić, and A. J. Horsewill, Phys. Rev. Lett. 113, 123001 (2014). L-4 QAMTS 2015 – Lectures Quantum tunneling of ultra-confined water A.I. Kolesnikov,1 L.M. Anovitz,1 G. Ehlers,1 E. Mamontov,1 A. Podlesnyak,1 T.R. Prisk,1 A. Seel,2 and G.F. Reiter3 1 2 Oak Ridge National Laboratory, PO Box 2008, Oak Ridge, TN 37831-6473, USA ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, UK 3 Physics Department, University of Houston, Houston, Texas 77204, USA Vibrational dynamics of ultra-confined water in single crystal beryl (space group P6/mcc), the structure of which contains ~5 Å diameter channels along the c-axis was studied with inelastic (INS), quasi-elastic (QENS) and deep inelastic (DINS) neutron scattering. The results reveal significantly anisotropic dynamical behavior of confined water, and show that effective potential experienced by water perpendicular to the channels is significantly softer than along them. The observed 7 peaks in the INS spectra (at energies 0.25 to 15 meV) can be explained by transitions between the split ground states of water in beryl due to water quantum tunneling between the 6fold equivalent positions across the channel. This water tunneling involves not only change positions of hydrogen atoms but also oxygen, and consequently water center of mass. Therefore, water tunneling in beryl is a unique phenomenon of quantum rotation-translation tunneling of relatively large particle (mass=18 a.u.). As a result of quantum tunneling water protons are delocalized over extended area (~1.2 Å) across the channel and exhibit narrow, anisotropic momentum distribution which was measured by DINS. The obtained average water proton kinetic energy, EK=95 meV, is much smaller than in bulk water (~150 meV), in spite of the observed almost highest possible O-H stretching modes of water in beryl. We believe that the narrow proton momentum distribution and exceptionally small kinetic energy for water protons in beryl are a result of water quantum tunneling/delocalization in the nanometer size confinements and weak water-cage interaction. L-5 QAMTS 2015 – Lectures Tunneling phenomena in simple molecular systems Attila G. Császár,1 Peter R. Schreiner,2 and Wesley D. Allen3 1 2 MTA-ELTE Complex Chemical Systems Research Group and Institute of Chemistry, Loránd Eötvös University, Pázmány Péter sétány 1/A, H-1117 Budapest, Hungary Institute für Organishe Chemie der Justus Liebig Universität, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany 3 Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA Tunneling phenomena in the simple molecular systems 14NH3 [1], HCOH [2], and (COOH)2 [3] are investigated via different theoretical, empirical, and experimental means. The MARVEL (Measured Active Rotational-Vibrational Energy Levels) approach [4] is used to study all the measured rovibrational transitions and the related energy levels of the 14NH3 molecule. The experimental-quality MARVEL energy levels reveal the wide-ranging effect of tunnelling on the rovibrational states of ammonia. The matrix isolation technique is used to capture trans-H–C–OH and subsequently infrared spectroscopy is employed to investigate its rearrangement reaction to formaldehyde. The same experimental technique is used to investigate a newly observed tunnelling phenomenon characterizing oxalic acid, domino tunnelling. High-level first-principles computations help to rationalize and quantitatively characterize the experimental results. The observed features of domino tunnelling exemplify the principle of tunnelling control, first observed in substituted hydroxycarbenes. Figure 1: Domino tunneling in oxalic acid. [1] A. R. Al-Derzi, T. Furtenbacher, J. Tennyson, S. Yurchenko, and A. G. Császár, J. Quant. Spectrosc. Rad. Transfer in press (2015), doi:10.1016/j.jqsrt.2015.03.034. [2] P. R. Schreiner, H. P. Reisenauer, F. C. Pickard, A. C. Simmonett, W. D. Allen, E. Mátyus, and A. G. Császár, Nature 453, 906 (2008). [3] P. R. Schreiner, J. P. Wagner, H. P. Reisenauer, D. Gerbig, D. Ley, J. Sarka, A. G. Császár, A. Vaughn, and W. D. Allen, J. Am. Chem. Soc. submitted for publication (2015). [4] T. Furtenbacher and A. G. Császár, J. Quant. Spectrosc. Rad. Transfer 113, 929 (2012). L-6 QAMTS 2015 – Lectures Quantum molecular tunneling in external electric and laser fields Jochen Küpper Center for Free-Electron Laser Science, DESY, Notkestrasse 85, 22607 Hamburg, Germany Department of Physics, University of Hamburg, Luruper Chaussee 149, 22761 Hamburg, Germany The Hamburg Center for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg, Germany The control of a sample’s initial state, e. g., the wave function of its constituent molecules, provides direct access to the quantum-mechanical properties and dynamics even for macroscopic samples. This control is beneficial, for instance, for experiments aimed at “recording the molecular movie”, i. e., the imaging of ultrafast molecular dynamics, using time-resolved coherent x-ray or electron diffractive imaging or photoelectron imaging, directly in the molecular frame. Appropriately shaped external dc or ac electric fields can be exploited to control the translational and rotational degrees of freedom of gas-phase molecules. Exploiting the quantum-state-specific manipulation of the translational motion, we have prepared neutral molecules in single rovibronic states [1–3] and we have separated them according to conformation [4, 5] or cluster size [6]. Laser fields allow to fix molecules in space, i. e., to align them or, through the combination of multiple fields, to orient them [7, 8]. Here, we will discuss the quantum dynamics involved in these processes. A non-resonant laser field provides a symmetric, double-minimum potential with a moderate barrier for the rotational degree of freedom of the molecules. The molecules are geometrically aligned in space due to confinement and tunneling in this potential. The addition of a dc electric field breaks the symmetry of the potential and leads to orientation. We have implemented these concepts for OCS molecules in a single rovibronic quantum state. Moreover, the creation of coherent wave packets allowed us to observe intruiging quantum dynamics in these artificial double-minimum potentials, such as a strongly driven quantum pendulum [9] and very strong dynamical orientation of molecules [10]. We will unravel the underlying physics, including the importance of nonadiabaticity in the formation of these wave packets. We will discuss that it is practically impossible to achieve fully adiabatic manipulation for larger molecules. Furthermore, such controlled molecules allow to directly image their structure in the molecular frame, including methods exploiting tunnel-ionization in strong laser fields [11–13], and I will discuss such experiments as time permits. [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] J. H. Nielsen, et al, Phys. Chem. Chem. Phys. 13, 18971 (2011), arXiv:1105.2413 [physics]. S. Putzke, et al, Phys. Chem. Chem. Phys. 13, 18962 (2011), arXiv:1103.5080 [physics]. D. A. Horke, et al, Angew. Chem. Int. Ed. 53, 11965 (2014). F. Filsinger, et al, Phys. Rev. Lett. 100, 133003 (2008), arXiv:0802.2795 [physics]. F. Filsinger, et al, Angew. Chem. Int. Ed. 48, 6900 (2009). S. Trippel, et al, Phys. Rev. A 86, 033202 (2012), arXiv:1208.4935 [physics]. H. Stapelfeldt and T. Seideman, Rev. Mod. Phys. 75, 543 (2003). B. Friedrich and D. Herschbach, J. Phys. Chem. A 103, 10280 (1999). S. Trippel, et al, Phys. Rev. A 89, 051401(R) (2014), arXiv:1401.6897 [quant-ph]. S. Trippel, et al, Phys. Rev. Lett. 114, 103003 (2015), arXiv:1409.2836 [quant-ph]. P. B. Corkum, Phys. Rev. Lett. 71, 1994 (1993). L. Holmegaard, et al, Nat. Phys. 6, 428 (2010), arXiv:1003.4634 [physics]. C. I. Blaga, et al, Nature 483, 194 (2012). L-7 QAMTS 2015 – Lectures Double hydrogen tunnelling in porphycenes: from condensed phases to isolated and single molecules Jacek Waluk Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, Poland; Faculty of Mathematics and Natural Sciences, College of Science, Cardinal Stefan Wyszyński University, Dewajtis 5, 01-815 Warsaw, Poland Porphycene, a constitutional isomer of porphyrin, emerges as a good model for studying intramolecular double hydrogen tunneling, due to exchange of two protons between nitrogen atoms that form an inner cavity (Figure 1). Tunneling occurs as a rate process in condensed phases, whereas for molecules isolated in supersonic jets or helium nanodroplets delocalization of the inner hydrogens is manifested by splitting of vibronic transitions, observed in absorption and fluorescence spectra [1]. These splittings are vibrational-mode-specific and different for ground and excited (S1) electronic states. For porphycenes in condensed phases, tautomerization rates can be obtained using polarized spectroscopy techniques. The process has been studied recently for a large family of porphycenes [2] and for single molecules, using fluorescence [3] and STM microscopies [4]. I will present new results of spectral and theoretical studies of porphycenes, focussing in particular on (i) changes in tunnelling splittings caused by minor perturbations; (ii) effects of coexcitation of vibrational modes that either promote or hinder tautomerization; (iii) modeling tunneling splittings by using 2D and 3D potentials; (iv) experimental evidence for the dominant role of tunnelling in condensed phases at elevated temperatures. N N N H H N N H H N N N Figure 1: Trans tautomers of parent, unsubstituted porphycene. [1] E. T. Mengesha, A. Zehnacker-Rentien, J. Sepioł, M. Kijak, and J. Waluk, J. Phys. Chem. B 119, 2193 (2015); E. T. Mengesha, J. Sepioł, P. Borowicz, and J. Waluk, J. Chem. Phys. 138, 174201 (2013). [2] P. Ciąćka, P. Fita, A. Listkowski, M. Kijak, S. Nonell, D. Kuzuhara, H. Yamada, C. Radzewicz, and J. Waluk, J. Phys. Chem. B 31, 149 (2004). [3] H. Piwoński, A. Sokołowski, M. Kijak, S. Nonell and J. Waluk, J. Phys. Chem. Lett. 4, 3967 (2013). [4] T. Kumagai, F. Hanke, S. Gawinkowski, J. Sharp, K. Kotsis, J. Waluk, M. Persson, and L. Grill, Phys. Rev. Lett. 111, 246101 (2013); Nature Chem. 6, 41 (2014). QAMTS 2015 – Lectures L-8 Tunneling in Intermolecular Carbene Reactions Stefan Henkel, Melanie Ertelt, Paolo Costa, Iris Trosien, Wolfram Sander Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, Germany Carbenes are among the most versatile reactive intermediates. Their reactivity can be controlled by substituents in a wide range from extremely electrophilic to radical-like to nucleophilic. The reactivity of carbenes can be utilized to activate otherwise rather inert molecules such as molecular hydrogen or water. In recent years we investigated a number of these reactions using matrix isolation spectroscopy.[1-6] Figure: Reaction of 4-oxocyclohexa-2,5-dienylidene with H2, HD, and D2 via tunneling. Tunneling reactions of a number of carbenes involving hydrogen activation (Figure) and proton transfer will be discussed in the lecture. [1] S. Henkel, W. Sander, Angew. Chem., Int. Ed. 2015, in print. [2] P. Costa, I. Trosien, M. Fernandez-Oliva, E. Sanchez-Garcia, W. Sander, Angew. Chem. Int. Ed. 2015, 54, 2656-2660. [3] S. Henkel, M. Ertelt, W. Sander, Chem. - Eur. J. 2014, 20, 7585-7588. [4] M. Ertelt, D. A. Hrovat, W. T. Borden, W. Sander, Chem. - Eur. J. 2014, 20, 4713-4720. [5] P. Costa, W. Sander, Angew. Chem., Int. Ed. 2014, 53, 5122-5125. [6] P. Costa, M. Fernandez-Oliva, E. Sanchez-Garcia, W. Sander, J. Am. Chem. Soc. 2014, 136, 1562515630. QAMTS 2015 – Lectures L-9 Dynamics of Intramolecular Hydrogen Transfer Reactions in Small Organic Molecules J.-M Mestdagh1, C. Crépin2, M. Chevalier2, A. Gutierrez-Quintanilla2, M. Briant1, L. Poisson1 1 2 Laboratoire Francis Perrin, URA 2453, CNRS, CEA, IRAMIS, LIDyL, F-91191 Gif-sur-Yvette, France Institut des Sciences Moléculaires d’Orsay, UMR 8214, CNRS, Université Paris-Sud, F-91405 Orsay, France Our groups at Institut des Sciences Moléculaires d’Orsay (ISMO) and Laboratoire Francis Perrin (LFP) collaborate for a long time in the field of intramolecular hydrogen transfer reactions with a focus given to the dynamics of the large-amplitude motion of an H-atom in organic molecules. The enol form of acetylacetone is almost a textbook example of a molecule with coupled large-amplitude motions. The coupling here is between the methyl group torsions and the intramolecular H-atom transfer from one O-atom to the other, mediated by the intramolecular H-bond. Experiments conducted at ISMO will be reported where the molecule was trapped in solid parahydrogen. Advantage was taken of the very slow nuclear spin conversion in the methyl groups to examine situations where the methyl group torsion is excited. This was used to shed light on the entanglement between the methyl torsion and the intramolecular hydrogen transfer [1]. Related works where glycolaldehyde is trapped in solid parahydrogen (ISMO) and helium nanodroplets (LFP) will be reported also. Time-resolved femtosecond pump-probe experiments were conducted at LFP, where the molecule under study is isolated in the gas phase. In these experiments electronic excitation by the pump laser induces dynamics where the electronic excitation is relaxed towards lower states, the excess energy being transformed as vibrational excitation of the molecule. Results will be presented on acetylacetone, indicating that an intramolecular vibrational energy relaxation is observed, which transfers excess vibrational energy from the enolic O-H group to the other modes of the molecule. Related works on 2H hydroxypyridine will be addressed also. O N [1] Lozada-Garcia, R. R.; Ceponkus, J.; Chevalier, M.; Chin, W.; Mestdagh, J.-M.; Crépin, C. Angew. Chem. Int. Ed. 2012, 51, 6947. QAMTS 2015 – Lectures L-10 Barrierless proton transfer across weak CH···O hydrogen bonds in dimethyl ether dimer Bruce L. Yoder,1 Ksenia B. Bravaya,2 Andras Bodi,3 and Ruth Signorell1 1 2 Laboratory of Physical Chemistry, ETH Zürich, Zürich, Switzerland Department of Chemistry, Boston University, Boston, Massachusetts, USA 3 Molecular Dynamics Group, Paul Scherrer Institut, Villigen, Switzerland Proton transfer is important in biological, chemical and atmospheric processes. Hydrogen bonds are known to facilitate inter- and intra-molecular proton transfer, in which the direction of the bond defines the reaction coordinate. The observation of protonated cluster fragments upon photoionization of molecular clusters is typically explained by fast intermolecular proton transfer occurring across hydrogen bonds.[1] Photoionization has been shown to produce protonated cluster fragments of several substances with traditional, strong intermolecular hydrogen bonds including water,[2-4] methanol,[5-7] and ammonia.[8] Weakly bound clusters are of interest for studying gas phase ionization-induced chemistry, as they fill the gap between strongly H-bonded systems and molecules interacting upon collision. We present a combined computational and threshold photoelectron photoion coincidence study of two isotopologues of dimethyl ether, (DME-h6)n and (DME-d6)n n = 1 and 2, in the 9– 14 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer, exhibiting various C–H···O interactions, were considered. All of which may be present in the experiment. Results from electronic structure calculations predict that all considered isomers undergo barrierless proton transfer upon photoionization to the ground electronic state of the cation. All neutral isomers were found to relax to the same radical cation structure. The lowest energy dissociative photoionization channel of the dimer leads to CH3OHCH3+ by the loss of CH2OCH3. Dimerization of dimethyl ether results in a 350 meV decrease of the valence band appearance energy and a nearly twofold increase in the ground state band width, compared with DME-d6 monomer. [1] [2] [3] [4] [5] S. Tomoda, Faraday Dis. 85, 53 (1988). O. Björneholm, F. Federmann, S. Kakar, and T. Möller, J. Chem. Phys. 111, 546 (1999). L. Belau, K. R. Wilson, S. R. Leone, and M. Ahmed, J. Phys. Chem. A 111, 10075 (2007). A. Bodi, J. Csontos, M. Kállay, S. Borkar, and B. Sztáray, Chem. Sci. 5, 3057 (2014). S. Martrenchard, G. Gregoire, C. Dedonder-Lardeux, C. Jouvet, and D. Solgadi, Phys. Chem. Comm. 2, 15 (1999). [6] S. Y. Lee, D. N. Shin, S. G. Cho, K. H. Jung, and K. W. Jung, J. Mass Spectrom. 30, 969 (1995). [7] O. Kostko, L. Belau, K. R. Wilson, and M. Ahmed, J. Phys. Chem. A 112, 9555 (2008). [8] S. T. Ceyer, P. W. Tiedemann, B. H. Mahan, and Y. T. Lee, J. Chem. Phys. 70, 14 (1979). L-11 QAMTS 2015 – Lectures A Theoretical Approach to Heavy Atom Tunneling: The Physical Limits for Reactivity and Selectivity Sebastian Kozuch Chemistry Department, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel Quantum mechanical tunneling of “heavy” atoms (i.e. carbon) was recently proven to be extremely atypical, but also exceptionally rich chemistry, especially at cryogenic conditions. The only requirements are a rather low activation energy and, much more important, a narrow barrier. Through the theoretical analysis (small curvature tunneling[1]) of the quantum tunneling driven reactions of: • • • Carbene ring expansions[2,3] Carbene formation from strained systems[4] Automerization of antiaromatic systems[5] we will evaluate the novel concepts of: • • • • Tunneling limit[3] Tunneling stability[4] Tunneling control of chemical reactions[2,6] Isotope controlled reactions Comparison with experimental values, predictions of reactivity and simple tests for quantum tunneling evaluation will be discussed. [1] A. Fernandez-Ramos, B. A. Ellingson, B. C. Garrett, and D. G. Truhlar, in Rev. Comput. Chem., edited by K. B. Lipkowitz and T. R. Cundari (John Wiley & Sons, Inc., 2007), pp. 125–232. [2] S. Kozuch, X. Zhang, D. A. Hrovat, and W. T. Borden, J. Am. Chem. Soc. 135, 17274 (2013). [3] S. Kozuch, Phys. Chem. Chem. Phys. 16, 7718 (2014). [4] S. Kozuch, Org. Lett. 16, 4102 (2014). [5] S. Kozuch, RSC Adv. 4, 21650 (2014). [6] D. Ley, D. Gerbig, and P. R. Schreiner, Org. Biomol. Chem. 10, 3781 (2012). L-12 QAMTS 2015 – Lectures Bio-inspired NMR Studies of Hydrogen Transfer and Bonding Hans-Heinrich Limbach Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany In the past decades, using liquid and solid state NMR, we have demonstrated the role of heavy atom motions preceding and during proton tunneling processes in organic model systems [1-3]. Recently, we have turned our attention to the modulation of strong low-barrier hydrogen bonds in complex environments. Bio-inspiered model systems derived from protein active sites as well enzymes are studied using various NMR methods, in particular combined UV/NMR spectroscopy. The following systems are discussed in this contribution: (1) Strong OHO Hydrogen Bonds of the Photoactive Yellow Protein [4-7]. (2) Strong OHN Hydrogen Bonds and Function of Aspartate-aminotransferase and Alanineracemase [8]. (3) Imidazole Tautomerism in the Active Site of Human Carbonic Anhydrase II [9]. We arrive at the following conclusions. Using combined UV/NMR and hydrogen bond correlations we can characterize single- and double well hydrogen bonds whose geometries are strongly influenced by the local environment, as confirmed by ab initio MD simulations [7]. Hydrogen bonded acid-base systems behave in enzyme active sites more like in polar wet organic solvents or in ionic liquids rather than in aqueous solutions. Strong critical hydrogen bonds are necessary to activate certain enzymes [8]. The tautomerism of imidazole clusters is catalyzed by some water molecules [9] and much faster than related pyrazole clusters [10]; moreover, imidazole behaves differently in water and in enzyme active sites, where it resembles again the behavior in wet polar organic solvents [9]. [1] H. H. Limbach, J. M. Lopez, A. Kohen, Phil. Trans. B (London). 361, 1399 (2006). [2] H. H. Limbach, in Hydrogen Transfer Reactions, J. T. Hynes, J. Klinman, H. H. Limbach, R. L. Schowen, Eds. Chapter Wiley-VCH, Weinheim 2007. Chapter 6, p. 135-221. Single and multiple hydrogen/deuterium transfer reactions in liquids and solids. [3] H. H. Limbach, K. B. Schowen, R. L. Schowen, J. Phys. Org. Chem. 23, 586 (2010). Special Issue Review Commentary Symposium on Tunneling. [4] H. H. Limbach, P. M. Tolstoy, N. Pérez-Hernández, J. Guo, I. G. Shenderovich, G. S. Denisov, Israel J. Chem. 49, 199 (2009). [5] B. Koeppe, Peter M. Tolstoy, H. H. Limbach, J. Am. Chem. Soc. 133, 7897 (2011). [6] B. Koeppe, J. Guo, P. M. Tolstoy, G. S. Denisov, H. H. Limbach, J. Am. Chem. Soc. 135, 7553 (2013). [7] Pylaeva, C. Allolio, B. Koeppe, G. S. Denisov, H. H. Limbach, D. Sebastiani, P. M. Tolstoy, Phys. Chem. Chem. Phys. 17, 17, 4634 (2015). [8] M. Chan-Huot, A. Dos, R. Zander, S. Sharif, P. M. Tolstoy, S. Compton, E. Fogle, M. D. Toney, I. G. Shenderovich, G. S. Denisov, H. H. Limbach, J. Am. Chem. Soc. 135, 18160 (2013). [9] I. G. Shenderovich, S. B. Lesnichin, C. Tu, D. N. Silverman, P. M. Tolstoy, G. S. Denisov, H. H. Limbach, Chem. Eur. Journal, 21, 2915 (2015). [10] O. Klein, F. Aguilar-Parrilla, J. M. Lopez del Amo, N. Jagerovic, J. Elguero, H. H. Limbach, J. Am. Chem. Soc. 126, 11718 (2004). QAMTS 2015 – Lectures L-13 The Haupt Effect in Solid-State NMR Beat H. Meier, Fabian Jähnig, Michael Batel, Marco Tomaselli, Anders B. Nielsen, and Matthias Ernst Physical Chemistry, ETH Zurich, 8092 Zurich, Switzerland A striking effect resulting from the strict correlation between the methyl rotational and nuclear spin states was discovered by Haupt who demonstrated that a large dynamic polarization, or ordering, of the proton spins with respect to the local dipolar field can be obtained after a sudden change in temperature of the solid.[1] The effect is largest for a methyl group with a low potential barrier for the methyl group rotation and can be explained by an interconversion of the tunnel-split A ( I = 3/2) and E ( I = 1/2) methyl spin isomers. [2,3]. The corresponding spin species have also been observed in solution state NMR after dissolution of a solid sample. [4] [5] [6]. We will discuss a number of applications in solid-state NMR including polarization transfer to other spin species and relaxation pathways involved in the buildup of the Haupt polarization which is still not fully understood. [1] [2] [3] [4] [5] [6] J. Haupt, New Effect of Dynamic Polarization in a Solid Obtained by Rapid Change of Temperature, Physics Letters A. A 38 (1972) 389–&. P. Beckmann, S. Clough, J. Hennel, J. Hill, Haupt Effect - Coupled Rotational and Dipolar Relaxation of Methyl-Groups, Journal of Physics C-Solid State Physics. 10 (1977) 729–742. M. Tomaselli, C. Degen, B.H. Meier, Haupt magnetic double resonance, J Chem Phys. 118 (2003) 8559–8562. M. Icker, P. Fricke, T. Grell, J. Hollenbach, H. Auer, S. Berger, Experimental boundaries of the quantum rotor induced polarization (QRIP) in liquid state NMR, Magn Reson Chem. 51 (2013) 815–820. doi:10.1002/mrc.4021. M. Icker, S. Berger, Unexpected multiplet patterns induced by the Haupt-effect, J Magn Reson. 219 (2012) 1–3. doi:10.1016/j.jmr.2012.03.021. B. Meier, J.-N. Dumez, G. Stevanato, J.T. Hill-Cousins, S.S. Roy, P. Hakansson, et al., LongLived Nuclear Spin States in Methyl Groups and Quantum-Rotor-Induced Polarization, J Am Chem Soc. 135 (2013) 18746–18749. doi:10.1021/ja410432f. QAMTS 2015 – Lectures L-14 Exact Quantum Dynamical Treatment of Hydrogen-material Interactions Jason McAfee,1 Megan Gonzalez,2 Adelia Aquino,2 and Bill Poirier2 1 Department of Chemistry, University of Texas, Dallas, Box 41061, 800 W Campbell, Richardson, TX 75080, USA 2 Department of Chemistry and Biochemistry, Texas Tech University, Box 41061, Lubbock, TX 79409-1061, USA This work investigates the fundamental quantum dynamical interactions of hydrogen with two specific material substrates: (1) (5,5) single-walled carbon nanotube (SWNT); (2) Fe(II)dihydride(dihydrogen) complex, Fe(H)2 (H2 )(PEtPh2 )3 . For the first system, the migration of exohedral H atom adsorbates is analyzed, addressing ramifications for hydrogen storage via catalytic spillover [1, 2]. Spin-polarized density functional theory (DFT) calculations are performed for a single adsorbate, and used to compute all bound rovibrational states [1]. This system exhibits a chemisorptive well-depth of 755 meV, which is unfavorable for spillover; however, a coherent quantum migration mechanism is revealed which may account for experimentally observed behavior. A subsequent DFT and quantum dynamics study under the more realistic conditions of full H-atom coverage is also performed [2]—characterized by a similar quantum migration effect, but also, overall energetics that are much more favorable to spillover. Finally, a preliminary investigation of the Fe(H)2 (H2 )(PEtPh2 )3 complex is conducted—specifically, of the full rotational motion of the dihydrogen ligand [3]. This motion is the most important dynamical player at low temperature, and is also expected to play an important role in the fluxional reorganization of the ligands via quantum tunneling. FIG. 1: Two hydrogen-material systems: (left) (H)n –SWNT; (right) Fe(H)2 (H2 )(PEtPh2 )3 . [1] J. L. McAfee and B. Poirier, J. Chem. Phys. 130, 064701 (2009). [2] J. L. McAfee and B. Poirier, J. Chem. Phys. 134, 074308 (2011). [3] N. Doslic, V. Gomzi, M. Malis, I Matanovic, and J. Eckert, Inorg. Chem. 50, 10740 (2011). L-15 QAMTS 2015 – Lectures Tunneling of open quantum systems: Nuclear spin isomers of molecules P.L. Chapovsky1,2 1 2 IAE SB RAS, prospect ak. Koptyuga Nr. 1, 630090 Novosibirsk, Russia Physics Department, Novosibirsk State University, 630090 Novosibirsk, Russia Symmetrical molecules with identical nuclei exist in Nature in the form of nuclear spin isomers. Well-known examples are the ortho and para isomers of H2, H2O, CH3F, etc. Spin isomers have fundamental importance and interesting applications in spectroscopy, NMR and astrophysics. In many applications the stability of spin isomers and mechanism of their relaxation is a key issue. Relaxation of spin isomers is rather complicated process. An interesting physical situation arises if the molecular environment is “nonmagnetic” and consequently cannot induce the isomer relaxation directly. In this case the isomer relaxation is caused by the intramolecular mixing of the isomer quantum states (tunnelling) and interruption of this mixing by interaction with the environment. This gives rise to a specific relaxation process that can be named quantum relaxation and should be distinguished from a standard one where an interaction with environment transfers the molecule directly from one isomer state to the other. Quantum relaxation of spin isomers is counterintuitive process. Despite of the strong isomer interaction with the environment the isomer relaxation is governed by the ortho-para state mixing produced by weak intramolecular forces that are intramolecular hyperfine interactions. In the talk we review the following aspects of the physics of nuclear spin isomers [1-8]: • Enrichment and relaxation of spin isomers in experiment. • Proofs of the validity of quantum relaxation of spin isomers. • Isomer enrichment and relaxation control by electromagnetic fields. • An access to weak interaction in molecules based on the isomer relaxation. • Isomer applications to NMR spectroscopy. • Search of the direct ortho-para transitions in molecules. 1. P.L. Chapovsky, A.D. Wilson-Gordon, J. Phys. Conf. Series, 594, 012003 (2015). 2. P.L.Chapovsky, V.V. Zhivonitko, I.V. Koptyug, J. Phys. Chem. A, 117, 9673 (2013). 3. V.V. Zhivonitko, et. al., Angew. Chem. Int. Ed. 52, 13251 (2013). 4. O.I. Permyakova, E. Ilisca, P.L. Chapovsky, Phys. Rev. A, 67, 033406 (2003). 5. P.L. Chapovsky, J. Phys. B, 34, 1123 (2001). 6. P.L. Chapovsky, L.J.F. Hermans, Annu. Rev. Phys. Chem., 50, 315 (1999). 7. B. Nagels, L.J.F. Hermans, P.L. Chapovsky, Phys. Rev. Lett., 79, 3097 (1997). 8. B. Nagels et. al., Phys. Rev. Lett., 77, 4732 (1996). L-16 QAMTS 2015 – Lectures Competing Excitonic Energy Transfer and Double Proton Transfer in the 7-Azaindole Dimer Philipp Ottiger,1 Zhifeng Xue,1 and Samuel Leutwyler1 1 Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, CH-3012 Bern, Switzerland The 7-azaindole molecule exhibits an NH donor and a pyridinic N acceptor site. In the supersonic-jet cooled dimer (7-azaindole)2 , (7AI)2 , the monomers are held coplanar and at a well-defined intermolecular distance by two symmetry-equivalent antiparallel NH· · · N hydrogen bonds, as illustrated in FIG. 1. This C2h symmetric H-bonded dimer has been widely investigated as a model system for excited-state double proton transfer (DPT). However, since the H-bonded (7AI)2 is C2h -symmetric, the two symmetry-equivalent S0 → S1 (ππ ∗ ) excitations of the 7AI monomers combine symmetrically and antisymmetrically, resulting in close-lying 1 Ag and 1 Bu states respectively. Thus, (7AI)2 exhibits both double proton exchange and excitonic energy exchange. In fact, both processes take place on very similar time scale (0.5–40 ps). While the excitonic energy transfer in (7AI∗ )2 is dominated by the dipole-dipole coupling between the two S0 → S1 transition dipole moments, the double proton transfer shows strong dependence on mass (H/D exchange) and on the intra- and intermolecular vibrational excitation in the S1 state. We discuss how the double proton transfer can be tuned to proceed faster or slower than the excitonic energy exchange by symmetrical or asymmetrical single or double deuteration. 4 13 3 5 C 9 2 N N H H N N R = 5.43 Å N N D N 1 H 7 N 8 6 q b) 7AI · 7AI-13C D N N d) (7AI-d)2 N D N D N D N D N N C e) 7AI-d · 7AI-d-13C FIG. 1: N D N 13 c) 7AI · 7AI-d N D N a) (7AI)2 f) 7AI-d · 7AI-d2 QAMTS 2015 – Lectures L-17 Diffusion Dynamics of Adsorbates: New Insight on Tunneling and Other Quantum Effects from an Old Formula Thiago Firmino,1 Roberto Marquardt,1, ∗ Fabien Gatti,2 and Wei Dong3 1 Laboratoire de Chimie Quantique - Institut de Chimie - UMR 7177 CNRS/UdS Université de Strasbourg 1, rue Blaise Pascal - BP 296/R8 - 67008 STRASBOURG CEDEX - France 2 CTMM, Institut Charles Gerhardt - UMR 5253 CNRS/Université de Montpellier 2 34095 MONTPELLIER Cedex 05 - France 3 Laboratoire de Chimie - UMR 5182 CNRS/Ecole Normale Supérieure de Lyon 46, Allée d’Italie, 69364 LYON Cedex 07 - France The formula proposed by van Hove in 1954 [1] for the dynamical structure factor (DSF) related to particle scattering at mobile adsorbates has recently been extended to the case when the adsobates’ excited states have finite lifetimes due to relaxation phenomena [2]. The new formula is evaluated quantum mechanically using wavefunctions, energies and lifetimes of vibrational states obtained for H/Pd(111) from first principle calculations. The results are capable of capturing qualitative features of diffusion rates measured for similar systems [3], if one assumes that the total rate obtained from the DSF is the sum of a diffusion and a friction rate. In this talk, we present the new formula and show how applications perform on similar systems. In particular we show that quantum effects such as tunneling and resonances might be important for the diffusion of adsorbates even at room temperature. [1] L. van Hove, Phys. Rev. 95, 249–262 (1954). [2] T. Firmino, R. Marquardt, F. Gatti, W. Dong, J. Phys. Chem. Lett. 5 4270-4274 (2014). [3] A. P. Jardine, G. Alexandrowicz, H. Hedgeland, W. Allison, J. Ellis, Phys. Chem. Chem. Phys. 11 3355-3374 (2009). ∗ corresponding author: [email protected] QAMTS 2015 – Lectures L-18 Tunneling Effects in Rotational Spectra of Water-Containing Complexes Elijah G. Schnitzler, Brandi L. M. Zenchyzen, Supriya Ghosh, Javix Thomas, Yunjie Xu, and Wolfgang Jäger Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive, Edmonton, AB T6G 2G2, Canada Studies of complexes and clusters that contain water molecules and an organic species are motivated by their role in elucidating structural and dynamical details in complex atmospheric processes or of hydrogen bonding effects in biological systems, for example. Hydrogen atoms of the water moiety in such complexes may undergo tunneling motions, regardless if hydrogenbonded or ‘free’. The water subunit can also affect internal tunneling motions of the other constituent, such as methyl internal rotation. In this presentation, I will discuss rotational, microwave spectroscopic and ab initio studies of several systems: benzoic acid – H2O (Figure 1), o-toluic acid – H2O, and oxalic acid – H2O are species of atmospheric significance and are thought to play a role as nucleation precursors in atmospheric aerosol formation. The study on methyl salicylate – H2O exemplifies, besides tunneling effects, the occurrence of structural isomers. In many cases, the spectroscopic analyses can result in detailed information about the tunneling motion, such as the tunneling barrier. In other cases, however, difficulties remain in interpreting observed fine structure splitting of rotational transitions in terms of specific tunneling motions. Figure 1: Possible tunneling motion in the benzoic acid – H2O dimer. L-19 QAMTS 2015 – Lectures Spin Isomers and Long-lived States: The crossover point from quantum rotors to room-temperature NMR Malcolm H Levitt1 1 University of Southampton, UK The phenomenon of spin isomerism is one of the most remarkable consequences of quantum mechanics: Heisenberg was awarded the Nobel prize for the prediction of two hydrogen allotropes (now known as the spin isomers parahydrogen and orthohydrogen) - a phenomenon which seemed incomprehensible to the chemists of the time. Spin isomers arise through the Pauli principle, which places strong constraints on the exchange symmetry of the complete quantum state, and hence strongly entangles the nuclear spin states with the spatial quantum states. For example, in a system like dihydrogen with two nuclear spins-1/2, the singlet nuclear spin state is associated with even rotational states (parahydrogen), while the triplet nuclear spin states are associated with odd rotational states (orthohydrogen). Similar phenomena exist in molecules such as water, and for quantum rotors such as freely rotating methyl groups in the cryogenic solid state. Results demonstrating a novel spin-isomer phenomenon will be shown: namely the slowly change in dielectric constant of a material containing encapsulated water, as ortho-water converts to para-water over the timescale of hours. Spin isomerism is associated with highly symmetrical, freely rotating molecules, or freelyrotating parts of molecules. However, some aspects of spin isomerism persist even for asymmetrical “ordinary” molecules in solution. The exchange symmetries which lead to spin isomerism may also give rise to the phenomenon of long-lived spin states, in which certain non-magnetic configurations of nuclear spin clusters persist for a long time. In some cases the lifetime of such long-lived states is more than 50 times faster than the relaxation time of ordinary nuclear magnetization. We have recently demonstrated a long-lived nuclear spin state which has a decay time constant exceeding 1 hour in room temperature solution. Such long-lived states may find applications in hyperpolarized NMR and magnetic resonance imaging. [1] G. Stevanato et al., “A Nuclear Singlet Lifetime of More than One Hour in Room-Temperature Solution”, Angew. Chem. Int. Ed. 54, 37403743 (2015). [2] S. Mamone et al., “Nuclear spin conversion of water inside fullerene cages detected by lowtemperature nuclear magnetic resonance”, J. Chem. Phys. 140, 194306 (2014). [3] M. H. Levitt, “Singlet Nuclear Magnetic Resonance”, Ann. Rev. Phys. Chem. 63, 89-105 (2012). QAMTS 2015 – Lectures L-20 Tunneling dynamics studied by high resolution FTIR/ THz spectroscopy with and without synchrotron light Sieghard Albert1, 2, Ziqiu Chen1, Philippe Lerch2 and Martin Quack1 1 Physical Chemistry, ETH Zurich, CH-8093 Zurich, Switzerland, 2 Swiss Light Source, PSI, CH-5232 Villigen, Switzerland The understanding of the dynamical behavior of functional groups like the hydroxyl (OH), the amino (NH2) or the aldehyde (CHO) group in biomolecules is essential for a complete understanding of their physical-chemical and biochemical kinetics. In particular, tunneling processes which are generally neglected in classical biomolecular dynamics modeling are in fact important and deserve study [1-15]. For that reason we have investigated the tunneling dynamics of phenol (C 6H5OH) [4], aniline (C6H5NH2) [5,6,7] and benzaldehyde (C6H5CHO) [5] as benchmark molecules using high resolution ( = 17 MHz) FTIR spectroscopy [8,9] without and with synchrotron radiation [4,5,10-12]. We were able to detect tunneling processes for phenol and aniline in the spectral range from 1 to 30 THz (33-1000 cm-1) and for benzaldehyde between 25 and 30 THz. The tunneling dynamics take place on a time scale on the order of 20 ns to 350 ps depending on the excitation of the vibrational modes. A particularly intriguing recent development is the theoretical prediction of tunneling switching in ortho- and meta-D-phenol (C6H4DOH) as opposed to phenol (C6H5OH) [4] where normal tunneling dominates the dynamics. For ortho- and meta-D-phenol at low energy, tunneling is completely suppressed due to isotopic substitution, which introduces an asymmetry in the effective potential. It effectively localizes the molecular wavefunction at either the syn or the anti-structure of ortho- and meta-D-phenol. At higher excited torsional states of ortho- and metaD-phenol, tunneling becomes dominant, thus switching the dynamics to a delocalized quantum wavefunction. We have been able to analyse the torsional fundamentals, the first and second overtones of both isotopomers by FTIR/THz and GHz [13] spectroscopy. A comparison of the spectra of phenol and ortho- and meta-D-phenol indicates the theoretically predicted behavior of tunneling switching upon excitation of the torsional mode. In detail, we shall discuss the splitting of the torsional fundamental, of the first and second overtones in phenol as well as the fundamentals of syn- and anti- ortho- and meta-D-phenol and the possible tunneling switching in torsional overtone region of ortho- and meta-D-phenol. The results shall be also discussed in relation to the quasiadiabatic channel reaction path Hamiltonian approach [14] including time dependent multidimensional wavepacket dynamics. The torsional dynamics in aniline is complicated due to the inversion dynamics which has already been analysed decades ago [15]. We have identified the two torsional components rovibrationally resolved due to inversion splitting in the torsional fundamental of aniline and have detected within each inversion-torsional component two bands. In addition, we have measured and analysed the inversion tunneling level at 40.95031 cm-1 and various excited tunneling levels. For benzaldehyde we detect torsional tunneling times in the ns range upon excitation of the in-plane-modes (600 to 1000 cm-1). If time permits we shall also discuss the spectroscopy of molecules that may be used for the detection of parity violation in relation to tunneling switching QAMTS 2015 – Lectures L-20 [1] M. Quack, Fundamental symmetries and symmetry violations from high resolution spectroscopy , in Handbook of High-Res. Spectroscopy, Vol. 1, (Eds. M. Quack and F. Merkt), Wiley, Chichester 2011, 659-722. [2] B. Fehrensen, D. Luckhaus and M. Quack, Z. Phys. Chem. 1999, 209, 1-19. [3] B. Fehrensen, D. Luckhaus and M. Quack, Chem. Phys. 2007, 338, 90-105. [4] S. Albert, Ph. Lerch, R. Prentner, M. Quack, Angew. Chem. Int. Ed. 2013, 52, 346-349. [5] S. Albert, K. Keppler Albert, Ph. Lerch and M. Quack, Highest resolution Fourier transform infrared (FTIR) spectroscopy of polyatomic molecules with and without synchrotron radiation in “Proceedings of the 18th Symposium on Atomic, Cluster and Surface Physics 2012 (SASP 2012)”, Alpe d’Huez, France, 22 to 27 January 2012”, pages 86 – 89, (Marius Lewerenz, Odile Dutuit, and Roberto Marquardt eds., Innsbruck University Press (IUP), Innsbruck, 2012), ISBN 978-3-902811-42-4. [6] E. Miloglyadov, R. Prentner, G. Seyfang, M. Quack, Inversion tunneling in normal and substituted anilines from infrared spectroscopy and quasiadiabatic channel reaction path Hamiltonian calculations in “Proceedings of the 18th Symposium on Atomic, Cluster and Surface Physics 2012 (SASP 2012)”, Alpe d’Huez, France, 22 to 27 January 2012”, pages 234 – 237, (Marius Lewerenz, Odile Dutuit, and Roberto Marquardt eds., Innsbruck University Press (IUP), Innsbruck, 2012), ISBN 978-3-902811-42-4. [7] M. Hippler, E. Miloglyadov, M. Quack, G. Seyfang, Mass and Isotope Selective Infrared Spectroscopy in Handbook of High Resolution Spectroscopy, Vol. 2 (Eds.: M. Quack, F. Merkt), Wiley, Chichester; New York, 2011, pp. 1069-1118. [8] S. Albert and M. Quack, ChemPhysChem. 2007, 8, 1271. [9] S. Albert, K.K. Albert, M. Quack, Fourier transform infrared spectroscopy, in Handbook of High-Res. Spectroscopy, Vol. 2, (Eds. M. Quack and F. Merkt), Wiley, Chichester 2011, 9651019. [10] S. Albert, K.K. Albert, Ph. Lerch, M. Quack, Faraday Discussions 2011, 150, 71-99. [11] S. Albert, Ph. Lerch and M. Quack. ChemPhysChem 2013, 14, 3204-3208. [12] S. Albert, K.K. Albert, Ph. Lerch, M. Quack, A. Wokaun, J. Mol. Spectrosc. 2015, in press. [13] Z. Chen, S. Albert, R. Prentner and M. Quack, paper at this meeting (QAMTS 2015). [14] R. Prentner, M. Quack, J. Stohner, M. Willeke, Faraday Discussions 2011, 150, 130-132. [15] M. Quack and M. Stockburger, J. Mol. Spectroscopy 1972, 43, 87-116. QAMTS 2015 – Lectures L-21 Atomic O diffusion on amorphous surfaces between 7 and 70 K: at what temperature does quantum tunneling dominate? Francois Dulieu,1 Marco Minissale,1 Emanuele Congiu,1 Henda Chaabouni and Saoud Baouche1 1 LERMA, Université de Cergy-Pontoise,(CNRS, Obs. de Paris, UPMC, ENS, PSL, Sorbonne Universités), 5 mail Gay Lussac, 95000 Cergy Pontoise, France When the density of interstellar clouds increases the interaction of the gas with the surface of dust grains becomes a major agent of the molecular evolution of the matter. During the last four years we have studied the physical and chemical properties of O atoms, the second reactive species in the interstellar medium, on cold (7 – 100 K) amorphous surfaces. At low temperatures, the interaction of adsorbates with passive amorphous surfaces is dominated by Van der Waals interactions. O can react with many others adsorbates (H, CO, H 2CO ...) and firstly among them, with itself. Therefore it is not straightforward to disentangle the diffusion from the reactivity of O. We have exposed different doses (from 5% of a layer to full coverage) of O(3P) atoms to various surfaces held at different temperatures. We observed the formation of O3 and O2 in variable amounts via IR spectroscopy or via Temperature Programmed Desorption. We performed a first set of experiment in the 6 – 25 K regime [1]. Assuming that the reactive system of O is diffusion-limited, we found that diffusion does not exhibit an Arrhenius dependency with the temperature, which would indicate a diffusion mediated by thermal hopping. On the contrary, the diffusion behaviour is very well fitted by a quantum tunnelling diffusion, although our model derived a rather high diffusion barrier (>500 K) and a low barrier width (0.7 Å). The quantum tunnelling diffusion is certainly an active process, and the question here is whether the critical temperature below which it's dominant with respect to thermal diffusion is actually as high as 20 K [2]. Recently, we have performed a new set of experiments focussed on the 40 – 70 K temperature range [3], in order to check if the all the indications found previously of high diffusion (and desorption) barriers were solid findings. We then proposed a new experimental method to directly derive the correlation between diffusion and desorption of reactive species. In this study we used a simple model based upon thermal diffusion. We find a very constrained set of couples of binding and diffusion energies. These “high temperature” couples of barriers, however, cannot explain the apparent diffusion and reactivity found at very low temperature. Finally, we have studied the diffusion and reactivity of O on amorphous surfaces between 7 and 70 K. This is an observation over one order of magnitude in temperature, and the scenario of the quantum tunnelling of O atoms at low temperatures still stands, and would deserve advanced theoretical studies to be pursued. [1] Minissale, M., Congiu, E., Baouche, S., Chaabouni, H., Moudens, A., Dulieu, F., … Pirronello, V. (2013). Quantum Tunneling of Oxygen Atoms on Very Cold Surfaces. Physical Review Letters, 111(5), 053201. doi:10.1103/PhysRevLett.111.053201 [2] Congiu, E., Minissale, M., Baouche, S., Chaabouni, H., Moudens, A., Cazaux, S., … Dulieu, F. (2014). Efficient diffusive mechanisms of O atoms at very low temperatures on surfaces of astrophysical interest. Faraday Discussions, 168, 151. doi:10.1039/C4FD00002A [3] Minissale, M., Congiu, Dulieu, F., Direct measurement of desorption and diffusion of O and N atoms physisorbed on amorphous surfaces Submitted to Physical Review Letters QAMTS 2015 – Lectures L-22 Jet-cooled high resolution infrared spectroscopy of molecular complexes P. Asselin1, Y. Berger1, P. Soulard1, M. Goubet2, T.R. Huet2, R. Georges3, O. Pirali4,5 1 Sorbonne Universités, UPMC Univ Paris 06, UMR 8233, MONARIS, F-75005, Paris, France CNRS, UMR 8233, MONARIS, F-75005, Paris, France 2 Laboratoire de Physique des Lasers, Atomes et Molécules, Bâtiment P5, UMR8523 Université Lille 1-CNRS, F-59655 Villeneuve d’Ascq Cedex, France 3 Institut de Physique de Rennes, Campus de Beaulieu, Bat 11C, UMR 6251, Université de Rennes 1-CNRS, 35042 Rennes Cedex, France 4 Ligne AILES- Synchrotron SOLEIL, L’Orme des Merisiers, F-91192 Gif/Yvette cedex, France. 5 Institut des Sciences Moléculaires d’Orsay, CNRS, Univ Paris-Sud, 91405 Orsay, France. For several decades, the implementation of the supersonic jet technique in the field of high resolution spectroscopy has opened the way to various experiments, in particular infrared absorption with Fourier Transform Spectroscopy (FTS) and lasers [1,2] . These studies enabled to characterize the intra- and intermolecular properties of non covalent systems, based on the many advantages provided by the supersonic expansion such as spectral simplification, sub-Doppler resolution and production of molecular sized clusters. A deeper knowledge of intermolecular hydrogen bonding interactions between several subunits, as for example within small HF-containing clusters or weakly bound complexes involving water, would require to collect accurate structural and vibrational dynamics data over a wider spectral range, namely by probing intermolecular modes and intramolecular proton donor bonded vibrations in the far- and mid-IR, respectively [3]. In this context, we are currently exploiting the complementary skills of two infrared probes for direct absorption: (i) the Jet-AILES set-up, a continuous supersonic free jet with high molar gas flows coupled to a high resolution FTS equipping the AILES beamline of the synchrotron light source SOLEIL, (ii) the SPIRALES set-up, a pulsed supersonic jet coupled to a tunable mid-IR external cavity quantum cascade laser (EC-QCL). Experimental details about FT broadband and laser narrowband spectroscopic set-ups will be given regarding to their respective performances in sensitivity and resolution, and to what bond strength and size of molecular systems can be dedicated this hydrogen bonded cluster research. Some illustrative examples of hydrogen bond studies realized in our team at Paris for one decade will be presented, focusing on recent results obtained with Jet-AILES in the mid-IR range about small hydrated hetero-clusters [4] and in the far–IR range about cyclic (HF)3 [5]. Preliminary results about van der Waals interactions between a rare gas (Rg) atom and a water molecule produced in pulsed supersonic expansions with a tunable QCL source will be also presented to highlight the strong potential of the rapid scan technique to investigate binary Rg-H2O complexes. References [1] D. J. Nesbitt, Ann. Rev. Phys. Chem. 45, 367 (1994). [2] J. Arno and J. W. Bevan, Jet spectroscopy and molecular dynamics, 1995 edited by J. M. Hollas and D. Philips (Edinburgh : Blackie). [3] A. Potapov and P. Asselin, Int. Rev. Phys. Chem. 33, 275 (2014). [4] M. Cirtog, P. Asselin, P. Soulard, B. Tremblay, B. Madebène et M. E. Alikhani, R. Georges, A. Moudens, M. Goubet, T.R. Huet, O. Pirali and P. Roy, J. Phys. Chem. A, 115, 2523 (2011). [5] P. Asselin, P. Soulard, B. Madebène, M. Goubet, T.R. Huet, R. Georges, O. Pirali and P. Roy, Phys. Chem. Chem. Phys. 16, 4797 (2014). QAMTS 2015 – Lectures L-23 Tunneling in molecules probed by high-resolution photoelectron spectroscopy Katrin Dulitz,1 Urs Hollenstein,1 Konstantina Vasilatou,1 and Frédéric Merkt1 1 Laboratorium für Physikalische Chemie, ETH Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland Removal of an electron from a stable and rigid neutral molecule often results in less stable and semi-rigid singly-charged cations which are subject to large-amplitude motion and quantum-mechanical tunneling. High-resolution photoelectron spectroscopy provides access to the structure and geometry of such cations. Moreover, the distribution of Franck-Condon factors favors the observation of the vibrational modes most strongly affected by the electron removal. We use pulsed-field ionization zero-kinetic-energy photoelectron spectroscopy to study largeamplitude motion in cations such as butatriene or cyclopropene in which photoionization is induced out of double bonds. The photoionization process in these molecules is of particular interest as it introduces torsional flexibility and quantum-mechanical tunneling between equivalent structures along the torsional coordinate. L-24 QAMTS 2015 – Lectures Computation of Molecular Parity Violation in View of Spectroscopic Experiments. Ľuboš Horný and Martin Quack Physical Chemistry, ETH Zürich, 8093 Zürich, Switzerland Measuring the parity violating energy difference Δ pvE between enantiomers of chiral molecules by spectroscopy is one of the frontiers of highest resolution molecular spectroscopy and a considerable challenge, which so far has not been successful[1-5]. Over the last decade, considerable progress has been made in the accurate theoretical description of molecular parity violation[6-9], its possible implications for the origin of molecular chirality and biomolecular homochirality, and its role in stereomutation dynamics of chiral molecules[1-5]. Accurate theoretical predictions of molecular parity violation importantly assist in a search for the most suitable molecular system, in which the fundamental requirement that the parity violating energy difference ΔpvE exceeds the tunneling splitting ΔE± in the ground state is fulfilled (Δ pvE >> ΔE±), and for which currently feasible experiments exist. We report calculations of the parity violating potentials Epv and point out the variety of their features with our recently developed coupledcluster singles and doubles linear response (CCSD-LR) approach [8,9] to electroweak quantum chemistry for variety of molecules. We present results for HOOH, and HSSH, which serve as test molecules for theory but are unsuitable for experiments because of large tunelling splittings in the ground state, and for ClOOCl, and fluoro- and chloro- substituted allenes, which are a possible candidates for experiment[9]. HSSSH[10] and 1,2-dithiin[11] were recently identified as ideal candidates for the proposed experiment following the scheme of [2]. Spectroscopic analysis is possible for 1,2-dithiin[11]. [1] M. Quack, Fundamental Symmetries and Symmetry Violations from High Resolution Spectroscopy, in Handbook of High-resolution Spectroscopy, edited by F. Merkt and M. Quack, (John Wiley & Sons, Ltd., Chichester, New York, 2011), pp. 659 − 772. [2] M. Quack, Chem. Phys. Lett., 1986, 132, 147-153. [3] M. Quack, Angew. Chem. Intl. Ed. (Engl.), 1989, 28, 571-586. [4] M. Quack, Angew. Chem. Intl. Ed. (Engl.), 2002, 41, 4618-4130. [5] M. Quack, J. Stohner and M. Willeke, Ann. Rev. Phys. Chem., 2008, 59, 741-769. [6] A. Bakasov, T. K. Ha and M. Quack, J. Chem. Phys., 1998, 109, 7263-7285. [7] R. Berger and M. Quack, J. Chem. Phys., 2000, 112, 3148-3158. [8] Ľ. Horný and M. Quack, Faraday Disc., 2011, 150, 152-154. [9] Ľ. Horný and M. Quack, Mol. Phys., 2015, doi: 10.1080/00268976.2015.1012131. [10] C. Fábri, Ľ. Horný and M. Quack, to be published and paper at this meeting. [11] S. Albert, Z. Chen, C. Fábri, Ľ. Horný and M. Quack, in preparation and paper at this meeting. QAMTS 2015 – Lectures L-25 Dynamic Effects in Enzyme Catalysis Louis Y. P.Luk, E. Joel Loveridge, Rudolf K. Allemann School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, United Kingdom. The role played by protein motions in enzyme-catalysed reactions has attracted much attention over recent years. The physical steps during enzyme catalysis -substrate binding, product release or other conformational changes- are well described in terms of ms-s timescale dynamics. Here we present a series of experimental and computational studies of dihydrofolate reductases from a psychrophile, a mesophile and two thermophiles to explore the role of protein motions for the actual chemistry. We describe an experimental method to identify specific regions of the enzyme whose motions affect the reaction on the timescales of both conformational changes and barrier crossings. Effects from DHFR dynamics on the chemical reaction are small at physiological temperatures but can increase dramatically at non-natural temperatures. Our results suggest that dynamic coupling to the chemical coordinate is detrimental to catalysis and may have been selected against during DHFR evolution. The full catalytic power of Nature’s catalysts appears to depend on finely tuning protein motions in each step of the catalytic cycle. QAMTS 2015 – Lectures L-26 Accelerating quantum instanton calculations of kinetic isotope e¤ects on tunneling rates Konstantin Karandashev1 and Jiµrí Vaníµcek1 1 Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland A convenient way to extract the extent of nuclear quantum e¤ects, such as many-dimensional tunneling, on the reaction rate constant is by measuring the kinetic isotope e¤ect. One approach to include the nuclear quantum e¤ects into rate calculation is via the quantuminstanton approximation [1], which was combined with the thermodynamic integration in order to compute the kinetic isotope e¤ect directly [2]. In practice, this approximation is evaluated via a path-integral Monte Carlo implementation, which is unfortunately computationally very expensive. In order to increase its e¢ ciency [3], we combine high-order factorization of the Feynman path integral [4], which accelerates the convergence to the quantum limit, with improved estimators [5], which accelerate statistical convergence of the Monte Carlo simulation. After demonstrating the improved e¢ ciency on the H + H H ! H H + H reaction, we apply the proposed method to evaluate several kinetic isotope e¤ects on the CH4 + H * ) CH3 + H2 forward and backward reactions. [1] [2] [3] [4] [5] W. H. Miller, Y. Zhao, M. Ceotto, and S. Yang, J. Chem. Phys. 119, 1329 (2003). J. Vaníµcek, W. H. Miller, J. F. Castillo, and F. J. Aoiz, J. Chem. Phys. 123, 054108 (2005). K. Karandashev and J. Vaníµcek, submitted. S. Jang, S. Jang, and G. A. Voth, J. Chem. Phys. 115, 7832 (2001). J. Vaníµcek and W. H. Miller, J. Chem. Phys. 127, 114309 (2007). QAMTS 2015 – Lectures L-27 KineticIsotopeEffectsasProbeforHydrogenTunnelinginEnzymes AmnonKohen Molecular and Cellular Biology The University of Iowa Kineticisotopeeffects(KIEs)andtheirtemperaturedependencecanserveaprobeforH‐ transferincomplexreactioncascades,suchasenzyme‐catalyzedreactions.The interpretationofexperimentaldatacansuggestaroleofquantummechanicalnuclear tunnelingofthehydrogentransferredinC‐HCandotherreactions.Moresignificantly,the datacansuggestarolefortheproteindynamicsinthepreparationofthetunnelingready state(TRS)priortotheH‐tunneling,andtherearrangementoftheheavyatomstowardthat state.Examplesindicatingwelldefineddonor‐acceptordistance(DAD)attheTRS,andsome suggestingbroaddistributionofDADsattheTRSwillbepresentedinthecontextofenzyme catalysisandevolution. L-28 QAMTS 2015 – Lectures Tunnelling in the Degenerate Rearrangement of Semibullvalene at Cryogenic Temperatures An Experimental Test of a Theoretical Prediction Melanie Ertelt,1 Stefan Henkel,1 Wolfram Sander,1 Xue Zhang,2 David A. Hrovat,2 and Weston Thatcher Borden*2 1 Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, Germany 2 Department of Chemistry and the Center for Advanced, Scientific Computing and Modeling, University of North Texas, 1155 Union Circle, #305070, Denton, Texas 76203-5070, USA CVT + TST calculations have predicted that the degenerate rearrangement of semibullvalene (1a) at cryogenic temperatures takes place with a temperature-independent rate constant of 2 x10-3 sec-1 [1]. It was proposed that this prediction could be tested by preparation of a mixture of semibullvalene-2-d1 (1b) and semibullvalene-4-d1 (1c), taking advantage of the facts that (a) the equilibrium constant between 1b and 1c should be temperature dependent; and (b) it should be possible to measure the concentrations of 1b and 1c in matrix isolation by IR. This prediction has now been tested by the synthesis of a mixture of 1,5-dimethylsemibullvalene-2-d1 (2a) and 4-d1 (2b). The results of experiments on the rate of equilibration of 2a and 2b at cryogenic temperature [2] will be described. [1] X. Zhang, D. A. Hrovat, and W. T. Borden, Organic Letters, 2010, 12, 2798, [2] Melanie Ertelt, Ph.D. thesis, Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, Germany, 2015. L-29 QAMTS 2015 – Lectures Concerted Electronic and Nuclear Fluxes During Coherent Tunneling Timm Bredtmann,1,2 Si-Dian Li,3 Jörn Manz,1,4 Wen-Juan Tian,3 Yan-Bo Wu,3 Yonggang Yang,1 and Hua-Jin Zhai3 1 State Key Laboratory of Quantum Optics and Quantum Optics Devices, Institute of Laser Spectroscopy, Shanxi University, Taiyuan 030006, China 2 3 Max-Born-Institut, Max-Born-Strasse 2a, 12489 Berlin, Germany Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China 4 Freie Universität Berlin, Takustrasse 3, 14195 Berlin, Germany This contribution to QAMTS is on coherent tunneling in molecules, from one configuration called "reactant" R to an equivalent one called "product" P. According to F. Hund, the quantum dynamics may be described in terms of the molecular tunneling dublett, with tunneling splitting ΔE and tunneling time τ where ΔE*τ = h [1]. Using this two-state model, we derive the related concerted electronic and nuclear fluxes along arbitrary symmetry-adapted sets of directions. For this purpose, we develop a new method for evaluating these fluxes, and for discovering their properties. For example, we present an analytical proof for the synchronicity of all fluxes. Moreover, we show that maximum absolute values of the fluxes are achieved at τ/4, half-way between R and P. The proof starts from the 3*Ne+3*Nn-dimensional continuity equation [2] which is then reduced to electronic and nuclear continuity equations for the fluxes along the chosen directions. For convenience, we define so-called main directions of the fluxes from the centers of the densities of R to P. Applications are to two model systems from inorganic and organic chemistry: the rhomb-to-rhomb isomerization of B4 and the Cope rearrangement of semibullvalene. The first case confirms chemical intuition i.e. core electrons flow with the nuclei, but valence electrons may flow in oblique directions. For the second case, our results suggest modifications of some traditional rules for pericyclic reactions. Our contribution extends previous work on electronic or nuclear fluxes, see e.g. references [3,4]. The present applications extend previous investigations of boron clusters and pericyclic reactions, for recent examples see references [5,6]. [1] F. Hund, Z. Phys. 43, 805-826 (1927) [2] E. Schrödinger, Ann. Phys. 384, 361-376 (1926). [3] I. Barth, H.–C. Hege, H. Ikeda, A. Kenfack, M. Koppitz, J. Manz, F. Marquardt, G. K. Paramonov, Chem. Phys. Lett. 481, 118-123 (2009). [4] I. Barth, C. Daniel, E. Gindensperger, J. Manz, J. F. Pérez-Torres, A. Schild, C. Stemmle, D. Sulzer, Y. Yang, Advances in Multi-Photon Processes and Spectroscopy, (Eds. S. H. Lin, A. A. Villaeys, Y. Fujimura), World scientific publication, Singapore, 22, 59-109 (2015). [5] H. J. Zhai, Y. F. Zhao, W. L. Li, Q. Chen, H. Bai, H. S. Hu, Z. A. Piazza, W. J. Tian, H. G. Lu, Y. B. Wu, Y. W. Mu, G. F. Wei, Z. P. Liu, J. Li, S. D. Li, L. S. Wang, Nat. Chem. 6, 727-731 (2014). [6] T. Bredtmann, J. Manz, Angew. Chem. Intern. Ed. 50, 12652-12654 (2011). L-30 QAMTS 2015 – Lectures Energy Landscapes: Prediction of Molecular Properties David J. Wales1 1 University Chemical Laboratories, Lensfield Road, Cambridge CB2 1EW, United Kingdom The potential energy landscape provides a conceptual and computational framework for investigating structure, dynamics and thermodynamics in atomic and molecular science. This talk will summarise new approaches for global optimisation, quantum dynamics, the thermodynamic properties of systems exhibiting broken ergodicity, and rare event dynamics. Applications will be presented that range from prediction and analysis of high-resolution spectra, to conformational changes of biomolecules and coarse-grained models of mesoscopic structures. [1] [2] [3] [4] [5] [6] D. J. Wales, Curr. Op. Struct. Biol., 20, 3-10 (2010) D. J. Wales, J. Chem. Phys., 130, 204111 (2009) B. Strodel and D. J. Wales, Chem. Phys. Lett., 466, 105-115 (2008) D. J. Wales and T. V. Bogdan, J. Phys. Chem. B, 110, 20765-20776 (2006) D. J. Wales, Int. Rev. Phys. Chem., 25, 237-282 (2006) D. J. Wales, “Energy Landscapes”, Cambridge University Press, Cambridge, 2003 L-31 QAMTS 2015 – Lectures Path Integral Metadynamics Prof. Michele Parrinello Department of Chemistry and Applied Biosciences, ETH Zurich, and Facoltà di Informatica, Istituto di Scienze Computazionali, Università della Svizzera Italiana, Via G. Buffi 13, 6900 Lugano, Switzerland [email protected] We develop a new efficient approach for the simulation of static properties of quantum systems using path integral molecular dynamics in combination with metadynamics. We use the isomorphism between a quantum system and a classical one in which a quantum particle is mapped into a ring polymer. A history dependent biasing potential is built as a function of the elastic energy of the isomorphic polymer. This enhances fluctuations in the shape and size of the ring in a controllable manner and allows escaping deep energy minima in a limited computer time. In this way we are able to sample high free energy regions and cross barriers, that would otherwise be insurmountable with unbiased methods. This substantially improves the ability of finding the global free energy minimum as well as exploring other metastable states. The performance of the new technique is demonstrated by illustrative applications on model potentials of varying complexity. L-32 QAMTS 2015 – Lectures Potential Energy Surfaces for Hydrogen in Porous Materials Probed by Rotational Tunneling Spectroscopy Tony Pham and Juergen Eckert Department of Chemistry, University of South Florida, Tampa, Fl. 33620, USA A detailed knowledge of the interactions responsible for binding hydrogen molecules in porous materials is essential for any further improvements of their hydrogen storage properties. Characterization of H 2 adsorption is almost exclusively carried by thermodynamic measurements, which only give average properties for all the sites occupied by H 2 molecules at a particular loading. One of the few molecular level experimental probes available is that of the observation of transitions between the hindered rotor energy levels of the adsorbed H2 by inelastic neutron scattering spectroscopy. The lowest of these transitions may be described as rotational tunneling, and its observation provides extraordinarily fine detail on the interaction of molecular hydrogen with porous host materials, particularly when analyzed in conjunction with computational analysis on the potential energy surfaces, which govern the H 2 quantum rotations. We have carried out an extensive series of computational studies on H 2 in several MOF’s employing a general purpose materials sorption potential along with explicit many-body polarization interactions. The latter assisted in the determination of the binding sites through the distribution of the induced dipoles that led to strong adsorbate interactions, and was crucial in obtaining an accurate representation of the observed rotational transition frequencies. The results of our systematic spectroscopic and computational studies on a large number of porous materials provide detailed information on the effectiveness of hydrogen binding at different types of sites, and thereby could give direction for efforts in the synthesis of new materials with improved hydrogen interactions with hybrid porous materials. QAMTS 2015 – Lectures L-33 Mass selective neutron spectroscopy M Krzystyniak1,2 1 ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX, UK School of Science and Technology, Nottingham Trent University, Clifton Campus, Nottingham NG11 8NS, UK 2 E-mail: [email protected] Neutron Compton scattering (NCS) technique Neutron Compton Scattering is a unique experimental technique made possible by the development of accelerator-based neutron sources, such as the ISIS source of the Rutherford Appleton Laboratory in the UK. The measurement of nuclear momenta by high-energy neutron Compton scattering relies on the fact that the energy and momentum transferred in the scattering process are sufficiently large, such that the so-called impulse approximation (IA) is an accurate starting point [1]. In the IA limit, the dynamic structure factor measured in NCS for a given nucleus covers the whole energy range of its motional modes. This includes translational and vibrational modes, followed by internal molecular vibrations and the whole spectral range of nucleus-projected vibrational density of states, in case of molecular systems and crystalline materials respectively. [1] Hence, if the IA is accurate, the deep inelastic-neutron-scattering response is related in a simple way to the nuclear momentum distributions (NMDs) of the nuclei. Thus, NCS is a unique technique enabling direct access to mean kinetic energy in a mass-selective manner. In principle, measurements on single-crystal specimens allow for the reconstruction of the proton wave function from NCS data in much the same way as crystal structures can be obtained from diffraction data. Conversely, comparison of experimental results from well-known benchmark molecular and condensed matter systems with ab initio computations provides an acid test for novel first-principles approaches to describe materials properties [2]. Since its birth, the NCS technique has been employed to study proton NMDs in quantum fluids and solids [3 - 11], metal hydrides [12 - 16] and gas, and charge-storage media [17], etc. Beyond the proton, recent instrument developments other the prospects of access to the NMDs of heavier nuclides including deuterium, helium, lithium, carbon, oxygen, and fluorine. [3, 4, 12, 13] As an inherently (and quite uniquely) mass-selective and non-destructive spectroscopic tool using neutrons, NCS can also provide information on sample composition, including hydrogen content in bulk materials [18]. At present, these measurements can only be performed in the aforementioned VESUVIO spectrometer in the United Kingdom. The work presented here seeks to fill the gap in the methodology of the determination of nuclear momentum distributions using epithermal neutrons by providing two specific examples of a direct and simultaneous access to the momentum distributions and mean kinetic energies of lightweight and heavy nuclei in two systems: (i) an ionic compound – lithium hydride and its deuterated counterpart, and (ii) squaric acid – an above room temperature organic antiferroelectric. It is demonstrated that, beyond the usual case of proton, the determination of the shapes of momentum distributions of heavier nuclei, deuterons and lithium, is also possible. Moreover, the paper demonstrates that, in case of oxygen and carbon, also kinetic energies can obtained directly from neutron Compton scattering experiments. On the scientific front, the presented data provide stringent benchmarks for first-principles calculations on these technologically relevant materials. From an instrumentation point of view, the presented experiments serve as preliminary assessment of current capabilities of mass-selective nuclear momentum distribution measurements (MANSE) of heavy nuclei using the electron-volt spectrometer VESUVIO at ISIS. [1] Andreani C, Colognesi D, Mayers J, Reiter G and Senesi R 2005 Adv. Phys. 55 377 [2] Lin L, Morrone J A, Car R and Parrinello M 2010 Phys. Rev. Lett. 105 110602 [3] Krzystyniak M 2010 J. Chem. Phys. 133 144505 [4] Krzystyniak M and Abdul-Redah T 2010 Phys. Rev. B 82 064301 [5] C-Dreismann C A, Abdul-Redah T and Krzystyniak M 2005 Phys. Rev. B 72 054123 [6] Abdul-Redah T, Krzystyniak M and C-Dreismann C A 2005 Phys. Rev. B 72 052202 [7] C-Dreismann C A and Krzystyniak M 2006 Journal of Physics: Condensed Matter 18 4741 [8] C-Dreismann C A and Krzystyniak M 2007 Phys. Rev. B 75 057102 [9] Krzystyniak M et al 2007 Journal of Chemical Physics 126 124501 [10] Krzystyniak M, et al 2008 Z. Anorg. Allg. Chem. 634 2056 [11] Krzystyniak M, et al. 2009 J. Phys.: Condens. Matter 21 075502 [12] Krzystyniak M and Fernandez-Alonso F 2011 Phys. Rev. B 83 134305 [13] Krzystyniak M, Richards S, Seel A and Fernandez-Alonso F 2013 Phys. Rev. B 88 184304 [14] Abdul-Redah T, Krzystyniak M and C-Dreismann C A 2005 Journal of Alloys and Compounds 404 790 [15] Abdul-Redah et al 2005 Journal of Alloys and Compounds 404 787 [16] Krzystyniak M and C-Dreismann C A 2007 J. Phys.: Condens. Matter 19 436321 [17] Krzystyniak M, Adams M A, Lovell A, Skipper N T, Bennington S M, Mayers J and Fernandez-Alonso F 2011 Faraday Discussions 151 171 [18] Mayers J and Reiter G 2012 Meas. Sci. Technol. 23 045902 L-34 QAMTS 2015 – Lectures The connection between the internal dynamics below and above the isomerization barrier for the [H,C,N] molecular system Georg Ch. Mellau,1 Alexandra A. Kyuberis,2 Oleg L. Polyansky,2, 3 Nikolai Zobov,2 and Robert W. Field4 1 Physikalisch-Chemisches 2 IAP, Institut, Justus-Liebig-Universität Giessen, Germany Russian Academy of Science, 46 Uljanov Street, Nizhny Novgorod, Russia 3 Department of Physics and Astronomy, UCL, Gower St, London, UK 4 Department of Chemistry, MIT, Cambridge, MA, USA The [H,C,N] molecular system is an important prototypical double well system of molecular physics. The bending states at the H-CN respective CN-H sides of the isomerization barrier merge into the internal rotation states of the hydrogen atom around the CN core as the excitation is increased above the isomerization barrier. In this work we study the connection between the internal dynamics above and below the isomerization barrier. Our eigenstate data set is a spectroscopically assigned eigenenergy spectrum [1] extended for this study up to 23000 cm−1 above the HCN minimum with stored state vectors. As the vibrational excitation energy approaches the isomerization barrier, the spacing of the vibrational energies shows a vibrational angular momentum dependent Dixon-dip-like trend [1], which correlates with the semiclassical pattern of the level spacings [2]. Based on the level spacings we can determine the dynamical proximity of an eigenstate to the effective dynamical isomerization barrier. The barrier proximal “saddle point states” are found to be highly localized [2] in the bending coordinate at the saddle point as expected from a semiclassical point of view. The localization takes place not only for pure bending states but also at all higher energies, exactly when the eigenenergies match the effective barrier height. The assignments of the levels above the barrier of isomerization connected to the localized states allows us to obtain the dynamical description of the internal rotation states. 800 0 0.2 HCN H0.5 CNH0.5 4 8 P 0.1 2 10 12 14 16 18 22 20 22 20 24 200 18 16 14 12 10 8 6 4 2 1 24 0v21 0 RH-CN γH-CN=76° 6 400 0 RH—CN HÅL HNC Dwvib Hcm-1 L 3 2 600 0 0 5000 10 000 Evib Hcm-1 L 15 000 20 000 0 45 ° 76 ° 90 ° gH—CN 135 ° 180 ° 0 45 ° 76 ° 90 ° 135 ° 180 ° gH—CN FIG. 1: Example for a localized state connecting the states above and below the barrier. [1] G. Ch. Mellau, J. Chem. Phys. 134, 234303 (2011). [2] J. Baraban et all., in prep. (2015). [3] G. Mellau, R. W. Field, O. L. Polyansky, A. Kyuberis, http://www.dpg-verhandlungen.de/ year/2015/conference/heidelberg/part/mo/session/20/contribution/4 (2015). L-35 QAMTS 2015 – Lectures Molecular Dynamics and Cluster Formation in Cold Helium Droplets Wolfgang E. Ernst1 1 Institute of Experimental Physics, Graz University of Technology, Petersgasse 16, 8010 Graz, Austria The unique experimental conditions provided by helium nanodroplets (HeN) are not only utilized in a special form of matrix isolation spectroscopy [1] but are also interesting for the study of molecular collisions in a superfluid solvent. Superfluid droplets of 104 to 107 helium atoms (HeN) are doped with one or several atoms or molecules that move freely in or on the droplets and may form complexes in this cold environment. Very weakly bound species and even unusual conformers are observed and can be investigated with any method that is commonly applied to molecular beams: laser spectroscopy and ionization, mass spectrometry, spin resonance, measurements in external electric or magnetic fields [1]. In this way, alkali and alkaline earth metal atoms that stay at the droplet surface were observed to react and form mixed diatomic molecules that were spectroscopically investigated over the whole visible spectrum [2-4]. Supported by our own quantum chemical calculations [5], these studies provide valuable information about this class of molecules that offers interesting prospects for ultracold molecular physics when they are produced from ultracold atoms in traps [6]. So far, little is known about molecular and cluster formation processes inside HeN. In a first test, we studied the Rb-Xe van der Waals system. As it turns out, the heliophobic Rb and heliophilic Xe are separated by helium through a barrier of about 18 cm-1[7]. Even two atoms of the same species residing on the same droplet, may be separated by a helium barrier if they are in different electronic states one of which is accommodated in the droplet and one at the surface. Such peculiar behaviour was observed for two chromium atoms with one in the a7S3 ground state and one in the a5S2 metastable state, both experimentally [8] and in DFT calculations [9]. Cold metal aggregates of different size can be generated in helium droplets, and even core-shell clusters with one metal surrounding a core of different kind are observed [10]. For the formation of mixed clusters, the time scales for the collisions in the cold helium solvent are of great interest. Applying helium density functional theory and molecular dynamics simulations, we recently derived collision times for the coinage metal atoms Cu, Ag and Au in He-droplets [11]. [1] C. Callegari and W. E. Ernst, in: Handbook of High Resolution Spectroscopy, Eds. F. Merkt and M. Quack, 1st Edition, Vol. 3, 1551-1594 (2011). [2] F. Lackner, G. Krois, T. Buchsteiner, J. V. Pototschnig, and W. E. Ernst, PRL 113, 153001 (2014). [3] G. Krois, F. Lackner, J. V. Pototschnig, T. Buchsteiner, and W. E. Ernst, PCCP 16, 22373 (2014). [4] J. V. Pototschnig, G. Krois, F. Lackner, and W. E. Ernst, J. Mol. Spectrosc. Online (2015). [5] J. V. Pototschnig, G. Krois, F. Lackner, and W. E. Ernst, J. Chem. Phys. 141, 234309 (2014). [6] B. Pasquiou, A. Bayerle, S.M. Tzanova, S. Stellmer, J. Szczepkowski, M. Parigger, R. Grimm, F. Schreck, Phys. Rev. A 88, 023601 (2013) [7] J. Poms, A W. Hauser, and W. E. Ernst, PCCP 14, 15158 (2012). [8] A. Kautsch, M. Koch, and W. E. Ernst, accepted by PCCP (2015). [9] M. Ratschek, J. V. Pototschnig, A. W. Hauser, W. E. Ernst, J. Phys. Chem. A 118 (33), 6622 (2014). [10] P. Thaler, A. Volk, F. Lackner, J Steurer, D. Knez, W Grogger, F Hofer, and W E. Ernst, Phys. Rev. B 90, 155442 (2014). [11] A. W. Hauser, A. Volk, P. Thaler and W E. Ernst, PCCP Advance Article online (2015). QAMTS 2015 – Lectures L-36 High-harmonic spectroscopy of attosecond quantum dynamics P. M. Kraus, D. Baykusheva, Ch. Roth, L. Horny and H. J. Wörner Laboratorium für physikalische Chemie, ETH Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland Strong-field ionization of molecules in the tunneling limit prepares coupled electronic and nuclear wave packets that evolve on attosecond to femtosecond time scales. These wave packets can be measured through photorecombination of the continuum electron with the parent ion, resulting in high-harmonic generation. The application of this method to the measurement of an attosecond electron-hole wavepacket in the iodoacetylene cation (ICCH+) will be presented. The hole dynamics is reconstructed from experimental measurements of high-harmonic emission from spatially-oriented molecules. The intense laser field is shown to efficiently control the electronic dynamics in molecules aligned parallel to the laser field. In contrast, the laser field is found to have no effect on the dynamics of molecules aligned perpendicular to the laser field, leading to the reconstruction of field-free charge migration. The solution of the time-dependent Schrödinger equation in a finite basis of electronic states supports these results. As a second example, the measurement of a coupled electronic-nuclear wave packet in the methane cation will be presented. The Jahn-Teller effect in CH 4+ drives an unusually fast structural rearrangement of the cation following strong-field ionization of CH4. This leads to the observation of a pronounced maximum in the ratio of autocorrelation functions of CD 4+ and CH4+ at a delay of 1.8 fs after ionization. This observation is supported by multi-configurational time-dependent Hartree calculations including all vibrational degrees of freedom. QAMTS 2015 – Lectures L-37 Benchmarking reaction kinetics astride the transition between the moderate and deep tunnelling regimes Simonetta Cavalli,1 Dario De Fazio, 2 and Vincenzo Aquilanti1,2,3 1Dipartimento 2Istituto di Chimica, Biologia e Biotecnologie dell’Università, 06123 Perugia, Italy di Struttura della Materia, Consiglio Nazionale delle Ricerche, Rome, Italy 2Instituto de Fisica, Universidade Federal da Bahia, Salvador, Brazil Recent attention to cold environments, either in the laboratory or under astrophysical and other conditions, is putting at the forefront the tunnel effect, a principal source of deviations from the Arrhenius rate law. Progress in theoretical chemical kinetics relies on accurate knowledge of potential energy surfaces, as provided by advanced quantum chemistry and tested against experiments. To generate accurate rate data, quantum scattering calculations involve sophisticated algorithms to produce scattering matrix elements at given angular momenta (to be summed to yield cross sections) and as a function of collision velocities (to be integrated to give rate constants and temperature dependencies). Here illustrated are these passages, a milestone having been benchmark temperature dependent rate constants for the prototypical F + H2 reaction [1], recently validated by experiments in the moderate tunnelling regime [2]. The F+ HD variant permits exploring tunnel as well as isotopic effects [3] and developing a phenomenology and interpretive ingredients down to the deep tunnelling regime [4-6]. Accurate data are becoming available for other reactions [7,8]. [1] V. Aquilanti, S. Cavalli, D. De Fazio, A. Volpi, A. Aguilar, J. M. Lucas “ Benchmark rate constants by the hyperquantization algorithm. The F + H2 reaction for various potential energy surfaces: features of the entrance channel and of the transition state, and low temperature reactivity” Chem. Phys. 308, 237-253 (2005) [2] M. Tizniti, S. D. Le Picard, F. Lique, C. Berteloite, A. Canosa, M. H. Alexander, I. R. Sims “The rate of the F + H2 reaction at very low temperatures”. Nature Chemistry., 6, 141–145 (2014) [3] D. De Fazio, V. Aquilanti, S. Cavalli, A. Aguilar, J. M. Lucas “Exact quantum calculations of the kinetic isotope effect: Cross sections and rate constants for the F + HD reaction and role of tunnelling” J.Chem. Phys. 125, 133109 (9 pages) (2006) [4] V. Aquilanti, K.C. Mundim, S. Cavalli, D. De Fazio, A. Aguilar, J. M. Lucas “Exact activation energies and phenomenological description of quantum tunneling for model potential energy surfaces. The F + H2 reaction at low temperature” Chemical Physics, 398,186-191 (2012) [5] V. H. C. Silva, V. Aquilanti, H. C. B. de Oliveira, K. C. Mundim “Uniform description of nonArrhenius temperature dependence of reaction rates, and a heuristic criterion for quantum tunneling vs classical non-extensive distribution” Chem.Phys.Letters, 590, 201-207 (2013) [6] S. Cavalli, V. Aquilanti, K. C. Mundim, D De Fazio “Theoretical reaction kinetics astride the transition between moderate and deep tunneling regimes: the F + HD case”, J Phys Chem A, 118, 6632–6641 (2014). [7] M. B. Krasilnikov, R. S. Popov, O. Roncero, D. De Fazio, S. Cavalli, V. Aquilanti, O. S. Vasyutinskii; “Polarization of molecular angular momentum in the chemical reactions Li+HF and F +HD” J. Chem. Phys. 138, 244302 (2013). [8] D. De Fazio, M. de Castro-Vitores, A. Aguado, V. Aquilanti, S. Cavalli “ The He + H2+ → HeH+ + H reaction: Ab initio studies of the potential energy surface, benchmark time-independent quantum dynamics in an extended energy range and comparison with experiments” J. Chem. Phys. 137, 244306 (2012) L-38 QAMTS 2015 – Lectures Quantum Mechanical Tunneling Reactions of Organic Reactive Intermediates Hiroshi Inui1, 2 and Robert J. McMahon2 1 Department of Chemistry, School of Science, Kitasato University, 1-15-1 Kitasato, Minami-ku, Sagamihara, Kanagawa 252-0373, Japan 2 Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, USA [email protected]; [email protected] Recent years have seen a burgeoning interest in chemical reactions that occur through reaction mechanisms involving quantum mechanical tunneling. We will describe examples, from our own research, that involve tunneling by heavy atoms and by hydrogen. Photodecomposition of 4-methylthiophenyl azide in matrixes at cryogenic temperatures generates a benzazirine intermediate, which was observed and identified on the basis of its IR spectrum. As expected, the benzazirine photochemically rearranges to the corresponding ketenimine and triplet nitrene. Interestingly, the rearrangement of benzazirine to ketenimine occurs in the dark at 10 K, despite a computed activation barrier of 3.4 kcal mol‒1.[1] Because this rate is 1057 times faster than that calculated for passing over the barrier, and because it shows no temperature dependence, the rearrangement mechanism is interpreted in terms of heavy-atom tunneling. Our research group maintains a longstanding interest in mechanisms of intramolecular hydrogen migration reactions in both organic and organometallic reactive intermediates.[24] In an inert matrix at low temperature, these intramolecular hydrogen migration reactions may be observed spectroscopically. These profiles reveal some interesting and puzzling trends. An unusual feature of these reactions is that they are spin-forbidden: the reactive intermediate is a triplet, while the hydrogen-migration product is a singlet. [1] [2] [3] [4] H. Inui, K. Sawada, S. Oishi, K. Ushida, R. J. McMahon, J. Am. Chem. Soc. 2013, 135, 10246-9. R. J. McMahon and O. L. Chapman, J. Am. Chem. Soc. 1987, 109, 683-692. T. M. Barnhart and R. J. McMahon, J. Am. Chem. Soc. 1992, 114, 5434-5435. S. W. Albrecht, Ph.D. Dissertation, University of Wisconsin-Madison 1995. QAMTS 2015 – Lectures L-39 Multiscale computational enzymology: Empirical Valence Bond simulation of benzylamine degradation catalyzed by monoamine oxidase Jernej Stare National Institute of Chemistry, Ljubljana, Slovenia Dopamine and serotonin are monoaminergic neurotransmitters present in the central nervous system. A detailed information of (pharmaco)kinetics of these systems on the molecular level is a key toward understanding of nerve signal transduction, function, pathology and pharmacological treatment of the central nervous system. The origin of neurodegenerative disorders such as Alzheimer and Parkinson disease can be traced to the metabolism of biogenic monoamines. Enzymes responsible for oxidative deamination of monoamine neurotransmitters and regulation of their level are called monoamine oxidases (MAO). The most crucial task required for a detailed understanding of the metabolism of monoamines is the characterization of the mechanism of oxidative deamination catalyzed by MAO, including the reaction free energy profile. Among the several proposed mechanisms supported by ab initio calculations, recent study shows evidence that the rate limiting step includes the C-H bond cleavage via hydride transfer from the monoamine substrate to the N5 atom of the flavin cofactor [1]. Proper assessment of factors governing the reaction is a challenging task, requiring accurate (quantum) description of the reactive part and inclusion of the complex fluctuating biomolecular environment. Among the available QM/MM protocols the Empirical Valence Bond (EVB) methodology [2] appears to be the method of choice, enabling simulation at least at a nanosecond timescale. Moreover, the approach facilitates the assessment of various effects related to enzymatic reactions, including point mutations, nuclear quantum effects, protonation states, inhibition, etc., at relatively low costs. It has been recently demonstrated that the EVB approach yields reliable results that are in good match with the experimental kinetic data on amines decomposed by MAO [3,4]. The presentation will include an overview of EVB and the related simulation methods applied to the MAO-catalysed decomposition of benzylamine, a structural analog of dopamine and similar monoamine neurotransmitters. Although not a biogenic substance, benzylamine is a suitable substrate of MAO undergoing the same mechanism of deamination; a variety of experimental kinetic data has been collected on benzylamine and its subsitituted analogs [5]. Factors governing the catalysis will be presented and critically discussed. Preliminary results concerning quantization of the nuclear motion and calculation of the H/D kinetic isotope effect will be also presented. References: [1] R. Vianello, M. Repič, J. Mavri, Eur. J. Org. Chem. 2012, 7057-7065. [2] J. Åqvist, A. Warshel, Chem. Rev. 1993, 93, 2523-2544. [3] M. Repič et al., Proteins 2014, 82, 3347-3355. [4] R. Borštnar et al., J. Chem. Theory Comput. 2012, 8, 3864-3870. [5] J. R. Miller, D. E. Edmondson, Biochemistry 1999, 38, 13670-13683. QAMTS 2015 – Lectures L-40 Quantum Mechanical Tunneling of Atoms in Water, Biochemistry and Astrochemistry T.P.M (Fedor) Goumans,1 Sonia Álvarez-Barcia,2 Judith B. Rommel,3 and Johannes Kästner3 1 Gorlaeus Laboratories, LIC, Leiden University, P.O. Box 9502, 2300 RA Leiden, Netherlands 2 3 Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain Institute for Theoretical Chemistry, University of Stuttgart, 70569 Stuttgart, Germany Quantum tunneling of hydrogen atoms is generally accepted to play a crucial role in hydrogen transfer reactions. We use instanton theory, based on statistical Feynman path integrals, to find the most probable tunneling path and the reaction rate. This is used to investigate the formation of H2 on the surface of carbonaceous dust grains in space [1] as well as the deuteration of interstellar methanol [2]. In water, tunneling causes a synchronization of the proton movement in Grotthuss chains [3]. Tunneling paths are also calculated for the decay of substituted singlet carbenes [4] and enzymatic reactions [5]. These simulations were made possible only through algorithmic improvements in the instanton optimization. We developed a quadratically-converging optimizer as well as an adaptive partitioning of the instanton path. Figure 1: Difference between the classical path (IRC) of a proton shuttle reaction and the dominant tunneling path (instanton). [1] T.P.M. Goumans, J. Kästner, Angew. Chem. Int. Ed. 49, 7350 (2010). [2] T.P.M. Goumans, J. Kästner, J. Phys. Chem. A 115, 10767 (2011). [3] S. Álvarez-Barcia, J.R. Flores, Johannes Kästner, J. Phys. Chem. A 118, 78 (2014). [4] J. Kästner, Chem. Eur. J. 19, 8207 (2013). [5] J B. Rommel, J. Kästner J. Am. Chem. Soc. 133, 10195 (2011). QAMTS 2015 – Lectures L-41 Ultrahigh resolution measurements of ro-vibrational- tunneling transitions in NH3: absolute frequencies and quadrupole splittings Peter Dietiker, Eduard Milogyadov, Martin Quack, Andreas Schneider, Georg Seyfang Physical Chemistry, ETH Zürich,CH- 8093 Zürich, Switzerland Ammonia has been a prototype molecule for tunnelling for a long time. In the present work we use ammonia as a prototypical test molecule for spectroscopic experiments on molecular parity violation. According to ordinary quantum chemistry including only the electromagnetic interaction the ground state energies of enantiomers of chiral molecules are exactly equal by symmetry. However, this symmetry is broken by the electroweak interaction and a slight energy difference ΔPVE is introduced between the ground states of the two enantiomers [1-7], the measurement of which is the final goal of our study. The aim of this work is to test both population transfer efficiencies and the ultimate resolution of the setup for the parity violation experiment. As a test molecule the achiral molecule NH3 has been chosen. The molecule has large rotational constants and only the lowest rotational levels (J = 0,1) are populated in a supersonic molecular beam. The absolute frequencies and quadrupole splittings of the ro-vibrational states of 1,3±1, 240 and 24±2 have been measured in a pump-probe experiment. A rovibrational state has been populated through the absorption of an IR-photon from a continuous wave OPO locked to a frequency comb. In the second step molecules prepared in the excited ro-vibrational level have been probed selectively by a 2+1 REMPI process through the electronically excited B-state (E”) or C-state (A1’). [1] M. Quack, Chem. Phys. Lett. 132, 147 (1986) [2] A. Bakasov, T.-K. Ha, M. Quack, J. Chem. Phys. 109, 7263 (1998) [3] R. Berger and M. Quack, J.Chem. Phys. 112, 3148 (2000) [4] M. Quack and J. Stohner, Phys. Rev. Lett. 84, 3807 (2000) [5] ] M. Quack and J. Stohner, J.Chem. Phys. 119, 11228 (2003) [6] M. Quack, J. Stohner, M. Willeke, Annu. Rev. Phys. Chem. 59, 741 (2008) [7] M. Quack, ‘Fundamental Symmetries and Symmetry Violations from High-resolution Spectroscopy’, in Handbook of High-resolution Spectroscopy, Vol.1, pages 659 – 722, M.Quack and F.Merkt (eds.), Wiley, Chichester 2011 QAMTS 2015 – Lectures L-42 Full-Dimensional Quantum Dynamics and Spectroscopy of Ammonia Isotopomers Csaba Fábri,1 Roberto Marquardt,1 and Martin Quack1 1 Physical Chemistry, ETH Zürich, 8093 Zürich, Switzerland Ammonia has been a prototype molecule for spectroscopy and quantum tunneling dynamics for a long time ([1,2] and references cited therein). Recently, accurate full-dimensional potential energy hypersurfaces have become available ([2,3] and references cited therein). In the present work we have applied and further developed the program GENIUSH ([4] and references therein) for the variational solution of the nuclear Schrödinger equation and the computation and interpretation of vibrational and rotational-vibrational energy levels and wave functions of ammonia isotopomers 14NH3, 14NHD2, 14NH2D, 14ND3, 14NHDT, 14NH2Mu, 14ND2Mu and 14NHDMu. The numerical construction of the general and exact kinetic energy operator allows the application of arbitrarily chosen internal coordinates and body-fixed frame embeddings (including the Eckart frame). Our up-to-date version of GENIUSH is able to employ a contracted vibrational basis set containing products of reduced-dimensional vibrational eigenfunctions, which facilitates the computation of highly-excited rovibrational eigenstates. Besides the computation of accurate rotational-vibrational energy levels and wave functions GENIUSH has been extended to include dynamics under coherent infrared multiphoton excitation [5]. [1] M. Snels, V. Horká-Zelenková, H. Hollenstein, M. Quack, High Resolution FTIR and Diode Laser Spectroscopy of Supersonic Jets in Handbook of High Resolution Spectroscopy, Vol. 2, pages 1021-1067, M. Quack, and F. Merkt, Eds. Wiley Chichester, 2011. [2] R. Marquardt and M. Quack, Global Analytical Potential Energy Surfaces for High Resolution Molecular Spectroscopy and Reaction Dynamics in Handbook of High Resolution Spectroscopy, Vol. 1, pages 511-549, M. Quack, and F. Merkt, Eds. Wiley Chichester, 2011. [3] R. Marquardt, K. Sagui, J. Zheng, W. Thiel, D. Luckhaus, S. Yurchenko, F. Mariotti and M. Quack, J. Phys. Chem. A 117, 7502 (2013). [4] A. G. Császár, C. Fábri, T. Szidarovszky, E. Mátyus, T. Furtenbacher and G. Czakó, Phys. Chem. Chem. Phys. 14, 1085 (2012). [5] M. Quack, Multiphoton Excitation, in Encyclopedia of Computational Chemistry, Vol. 3, pages 1775-1791, P. v. R. Schleyer et al, Eds. Wiley Chichester, 1998. L-43 QAMTS 2015 – Lectures Generation of Higher-Energy Conformers and Proton Tunneling in Matrix-Isolated Molecules Containing OH group Igor Reva Department of Chemistry, University of Coimbra, Rua Larga, 3004-535 Coimbra, Portugal This contribution will cover some experimental results obtained over the past few years, with focus on proton tunneling in molecules containing OH group. Selected molecules were isolated in cryogenic matrices and were characterized by vibrational spectroscopy in mid-infrared and near-infrared domains. Using tunable narrow-band (fwhm < 1 cm−1) near-infrared light, it was possible to excite in situ, in a very selective way, only molecules adopting a particular conformation. Usually it concerned excitation of an overtone of OH stretching vibration, absorbing in the 7000-6600 cm−1 range. Such excitations provided studied molecules with energy higher than the OH torsional barrier, and afforded generation of new higher-energy conformers in the course of vibrational energy redistribution to the OH torsional coordinates. The studied systems include nucleic acid base cytosine [1], a few 5-substituted cytosines [2], natural amino acid alanine [3], as well as several carboxylic acids: squaric [4], glycolic [5], tetrazole-acetic [6], furoic [7], oxamic [8], and pyruvic [9]. For all these molecules, new, previously unknown higher-energy conformers were generated and spectroscopically characterized. A spontaneous conversion of these higher-energy conformers into their more stable counterparts, via proton tunneling, was also studied. The dependence of the decay kinetics on the matrix gas material (Ne, Ar, N2), presence or absence of external light, and also on the sample temperature will be discussed. Acknowledgements: This work was supported by the Portuguese “Fundação para a Ciência e a Tecnologia” (FCT), via Programa Investigador FCT, Research Project PTDC/QUI-QUI/118078/2010, FCOMP-01-0124-FEDER-021082, co-funded by QREN-COMPETE-UE. The Coimbra Chemistry Centre is supported by FCT project Pest-OE/QUI/UI0313/2014. The support from bilateral project No. 2505 for cooperation between Poland and Portugal is also acknowledged. References: [1] I. Reva, M. J. Nowak, L. Lapinski, and R. Fausto, J. Chem. Phys. 136, 064511 (2012). [2] L. Lapinski, I. Reva, H. Rostkowska, R. Fausto, and M.J. Nowak, J. Phys. Chem. B 118, 2831 (2014). [3] C. M. Nunes, L. Lapinski, R. Fausto, and I. Reva, J. Chem. Phys. 138, 125101 (2013). [4] L. Lapinski, I. Reva, H. Rostkowska, A. Halasa, R. Fausto, and M. J. Nowak, J. Phys. Chem. A 117, 5251 (2013). [5] A. Halasa, L. Lapinski, I. Reva, H. Rostkowska, R. Fausto, and M. J. Nowak, J. Phys. Chem. A 118, 5626 (2014). [6] C. Araujo-Andrade, I. Reva, and R. Fausto, J. Chem. Phys. 140, 064306 (2014). [7] A. Halasa, L. Lapinski, I. Reva, H. Rostkowska, R. Fausto, and M. J. Nowak, J. Phys. Chem. A 119, 1037 (2015). [8] A. Halasa, L. Lapinski, H. Rostkowska, I. Reva, and M.J. Nowak, J. Phys. Chem. A 119, 2203 (2015). [9] I. Reva, C. M. Nunes, M. Biczysko, and R. Fausto, J. Phys. Chem. A 119, 2614 (2015). QAMTS 2015 – Poster contributions P-1 MOGADOC Database Update: Diversity of Molecular Structures with Large-Amplitude Motion, Tunnelling and Other Effects Natalja Vogt, Rainer Rudert, and Jürgen Vogt Chemical Information Systems, University of Ulm, D-89069, Germany The MOGADOC database (Molecular Gas-Phase Documentation) has grown up to 11,500 inorganic, organic, and organometallic compounds, which were studied in the gas-phase mainly by microwave spectroscopy, electron diffraction, and radio astronomy and published in about 39,500 papers. This literature is recorded back to the very beginning of each method. The database informs about structural, dynamic (including large-amplitude motions, tunnelling, etc.), electric, magnetic, and other properties. Among them the structural parameters such as internuclear distances, bond and dihedral angles are given numerically for 9,200 structures, which have been excerpted from the literature and critically evaluated, whereas the remaining properties can only be retrieved by keyword search terms. The retrieval features of the HTML-based database have been described elsewhere [1-2]. The molecular structures can be visualized in three dimensions by means of a specially developed Java-applet. The user can interactively rotate and “measure” these 3-D models [3]. The project has been supported by the Dr. Barbara Mez-Starck Foundation. [1] J. Vogt, N. Vogt, and R. Kramer, J. Chem. Inf. Comput. Sci. 43, 357 (2003). [2] J. Vogt and N. Vogt, J. Mol. Struct. 695, 237 (2004). [3] N. Vogt, E. Popov, R. Rudert, R. Kramer, and J. Vogt, J. Mol. Struct. 978, 201 (2010). P-2 QAMTS 2015 – Poster contributions Quantum Tunneling in the Hydrogenation of Singlet and Triplet Carbenes Probed by Matrix Isolation Spectroscopy Stefan Henkel and Wolfram Sander Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum Universitätsstraße 150, 44801 Bochum, Germany In the quest for probing reaction intermediates the matrix-isolation technique has proven to be a powerful tool to investigate structure and reactivity of otherwise hardly accessible species. In addition, the low-temperature conditions of the matrix suppress any thermal reaction that has an activation barrier higher than a few calories and therefore allows to probe for reactions involving quantum-mechanical tunneling. We used this technique to investigate the hydrogenation reaction of carbenes in hydrogen-doped argon as well as in pure hydrogen matrices at 3 - 30 K. D H D H H H H2 (HD, D2) 3K D 1 D H H2 (HD, D2) H H +H 3K O 2 O O While the reaction mechanism of the hydrogenation depends on the electronic ground-state of the carbene, we found that for both, singlet and triplet carbenes, quantum tunneling can dominate the reaction at low temperatures. Thus, singlet 1-azulenylmethylene 1 [1] and triplet oxocyclohexadienylidene 2 [2] readily react with H2 and HD at 3 K. In contrast, a large kinetic isotope effect is observed for the reaction with deuterium for both carbenes, consistent with a tunneling controlled reaction. [1] S. Henkel, W. Sander, Angew. Chem. Int. Ed. 54 (2015). [2] S. Henkel, M. Ertelt, W. Sander, Chem. Eur. J. 20, 7585 (2014). QAMTS 2015 – Poster contributions P-3 Valence-shell-photoelectron imaging of complex molecules Joss Wiese,1 Sebastian H. Trippel,1 and Jochen Küpper1, 2, 3 1 Center for Free-Electron Laser Science, DESY, Notkestrasse 85, 22607 Hamburg, Germany 2 Department of Physics, University of Hamburg, Luruper Chaussee 149, 22761 Hamburg, Germany 3 The Hamburg Center for Ultrafast Imaging, University of Hamburg, Luruper Chaussee 149, 22761 Hamburg, Germany A molecule’s chemical behaviour is governed by its electronic properties. Thus, a view at the evolution of the involved molecular orbitals during a chemical reaction lures with insight into the fundamentals of chemistry. Here, we report on the investigation of the electronic structure of complex molecules using strong-field-ionization photo-electron imaging in the molecular frame. State-selected molecular ensembles [2] are three-dimensionally laser aligned or mixed-field oriented inside a velocity map imaging spectrometer [3–6]. The electron velocity maps of strong-field-ionized electrons display the projected three dimensional distributions of both, the electrons’ kinetic energy and their release angle, in the molecular frame (MFPADs) [1]. MFPADs of some polyatomic molecules and molecular clusters will be discussed in terms of the molecular orbitals which are involved in the ionization process. Three dimensional MFPADs will be presented, which were obtained through tomographic reconstruction of the projected 2D images [7]. [1] L. Holmegaard, J. L. Hansen, L. Kalhøj, S. L. Kragh, H. Stapelfeldt, F. Filsinger, J. Küpper, G. Meijer, D. Dimitrovski, M. Abu-samha, C. P. J. Martiny, and L. B. Madsen, Nat. Phys. 6, 428 (2010), arXiv:1003.4634 [physics]. [2] S. Trippel, Y.-P. Chang, S. Stern, T. Mullins, L. Holmegaard, and J. Küpper, Phys. Rev. A 86, 033202 (2012), arXiv:1208.4935 [physics]. [3] H. Stapelfeldt and T. Seideman, Rev. Mod. Phys. 75, 543 (2003). [4] L. Holmegaard, J. H. Nielsen, I. Nevo, H. Stapelfeldt, F. Filsinger, J. Küpper, and G. Meijer, Phys. Rev. Lett. 102, 023001 (2009), arXiv:0810.2307 [physics.chem-ph]. [5] I. Nevo, L. Holmegaard, J. H. Nielsen, J. L. Hansen, H. Stapelfeldt, F. Filsinger, G. Meijer, and J. Küpper, Phys. Chem. Chem. Phys. 11, 9912 (2009), arXiv:0906.2971 [physics]. [6] S. Trippel, T. Mullins, N. L. M. Müller, J. S. Kienitz, K. Długołęcki, and J. Küpper, Mol. Phys. 111, 1738 (2013), arXiv:1301.1826 [physics.atom-ph]. [7] J. Maurer, D. Dimitrovski, L. Christensen, L. B. Madsen, and H. Stapelfeldt, Phys. Rev. Lett. 109, 123001 (2012). QAMTS 2015 – Poster contributions P-4 Tunneling as a Source of Hyperpolarization in Nuclear Magnetic Resonance F. Jähnig, A. B. Nielsen, B. H. Meier, and M. Ernst ETH Zürich, Physical Chemistry, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland Since its early days Nuclear Magnetic Resonance (NMR) suffers from low sensitivity and consequently a lot of techniques have been developed to enhance sensitivity. As NMR measures population differences between different spin states of nuclei, called polarization, multiple ways to increase this polarization were developed to boost the signal-to-noise ratio. Today the term hyperpolarization embraces all efforts that lead to polarization larger than the thermal-equilibrium polarization. One of these methods termed 'Haupt-Effect' relies on the coupling of the spin states and the rotational states in methyl groups to generate hyperpolarization [1]. In contrast to other hyperpolarization methods, no additional polarizing agent has to be introduced to the sample to observe the polarization enhancement in the Haupt effect [2,3]. Using the Haupt effect, spin hyperpolarizion is generated by cooling the target molecule below 5 K followed by rapidly heating to a temperature typically around 40 K. While the motion of methyl groups at higher temperatures can be described by a classical jump model it is better described by a tunneling motion at low temperatures. The Haupt effect might stimulate interesting applications in the future if the Haupt polarization can be efficiently utilized [4]. This contribution will illustrate the general mechanism of the Haupt effect and highlight some work in this area done in our laboratory. Our interest focused on a theoretical description of nuclear spin relaxation in rotating methyl groups in the solid state. We have developed a comprehensive relaxation description of all coupled relaxation modes in such a system taking into account CSA and dipolar relaxation under stochastic rotations with and without the tunneling splitting. Data from low temperature relaxation experiments on 13C-labeled as well as unlabeled Li-Acetate will be shown. On this data a model of the motion is built which aims to explain the relaxation behaviour of the methyl groups. Further we present data from temperature jump experiments on the same samples which is analyzed using the model of the methyl motion from the relaxation data. [1] [2] [3] [4] J. Haupt, Z. Naturforschung 28a, 98-104, (1973) A.J. Horsewill, Progr. Nucl. Magn. Reson. Spectrosc. 35, 359-389, (1999) M. Icker, S. Berger, J. Magn. Reson. 219, 1-3, (2012) S.S. Roy, J.Dumez, G. Stevanato, B. Meier, J.T. Hill-Cousins, R. C.D. Brown, G. Pileio, M.H. Levitt, J. Magn. Reson. 250, 25-28, (2015) QAMTS 2015 – Poster contributions P-5 Modulation Techniques in Vacuum-Ultraviolet High-Resolution Absorption Spectroscopy U. Hollenstein,1 H. Schmutz,1 and F. Merkt1 1 Laboratorium für Physikalische Chemie, ETH Zürich, CH-8093 Zürich, Switzerland High-resolution absorption spectroscopy in the vacuum (λ < 200 nm; VUV) and extreme (λ < 105 nm; XUV) ultraviolet ranges of the electromagnetic spectrum is notoriously difficult. VUV radiation from synchrotron sources needs to be monochromatised, which limits the bandwidth of the radiation to at best 0.1 cm−1 [1]. VUV-FT absorption spectroscopy, as recently extended to the XUV range offers the multiplex advantage, but so far the best resolution achieved with this method is 0.33 cm−1 [2]. Pulsed VUV laser systems based on four-wave mixing enable a higher resolution [3], but the large pulse-to-pulse fluctuations resulting from the non-linearity of the VUV generation process limits the sensitivity of absorption measurements, so that only very few laser VUV absorption spectra of atoms and molecules in supersonic beams have been reported [3, 4]. To improve the low sensitivity resulting from the large pulse-to-pulse fluctuation of the VUV radiation, Sommavilla et al. [5] have used a dispersion grating and exploited the beam diffraction in the negative first order to normalise the VUV laser intensity pulse by pulse and were able to reliably measure absorption signals of 104 . We present here an alternative method to record absorption spectra with high sensitivity that relies on frequency modulation techniques. The VUV radiation is produced by two-photon resonance-enhanced (ν̃VUV = 2ν̃1 ± ν̃2 ) four-wave mixing in Kr using the 1 S0 → 4p5 5p[1/2](J = 0) resonance at 2ν̃1 = 94 092.96 cm−1 using the output of two FT-limited pulsed lasers (pulse length 5 ns, obtained by pulse amplification of cw ring laser radiation). The modulation of the VUV laser frequency is achieved by generating side bands on the output of the second laser (ν̃2 ) using an electro optical modulator. These side bands are automatically transferred to the VUV because the four-wave mixing process is linearly dependent on the intensity of the second laser. [1] Laurent Nahon, Christian Alcaraz, Jean-Louis Marlats, Bruno Lagarde, Fran cois Polack, Roland Thissen, Didier Lepère and Kenji Ito, Rev. Sci. Instr. 72, 1320 (2001). [2] N. de Oliveira, D. Joyeux, D. Phalippou, J. C. Rodier, F. Polack, M. Vervloet and L. Nahon, Rev. Sci. Instr. 80, 043101 (2009). [3] P. C. Hinnen, S. Stolte, W. Hogervorst and W. Ubachs, J. Opt. Soc. Am. B 15, 2620 (1998). [4] T. P. Softley, W. E. Ernst, L. M. Tashiro and R. N. Zare, Chem. Phys. 116, 299 (1987). [5] M. Sommavilla, U. Hollenstein, G. M. Greetham and F. Merkt, J. Phys. B: At. Mol. Opt. Phys. 35, 3901 (2002). QAMTS 2015 – Poster contributions P-6 Tunneling and Parity Violation in Trisulfane (HSSSH): An Almost Ideal Molecule for Detecting Parity Violation in Chiral Molecules Csaba Fábri,1 Ľuboš Horný,1 and Martin Quack1 1Physical Chemistry, ETH Zürich, 8093 Zürich, Switzerland Measuring the parity-violating energy difference ΔpvE between enantiomers of chiral molecules by spectroscopy is one of the frontiers of highest resolution molecular spectroscopy and a considerable challenge, which so far has not been met with success [1-5]. Over the last decade, considerable progress has been made in the accurate theoretical description of molecular parity violation [6-8], its possible implications for the origin of molecular chirality and biomolecular homochirality, and its role in the stereomutation dynamics of chiral molecules [1-5]. Accurate theoretical predictions of molecular parity violation importantly assist in a search for the most suitable molecular system. At the same time, tunneling must be studied for candidate molecules, as one must have ΔpvE >> ΔE± (the tunneling splitting for the symmetrical case). In this work we investigate the stereomutation tunneling process in the HSSSH molecule. We report calculations of the parity-violating potential and the ground-state tunneling splitting employing different one- and two-dimensional vibrational Hamiltonians. Our computations utilized the quasi-adiabatic channel reaction path Hamiltonian method [9], the general rotational-vibrational GENIUSH program package [10] and our recently developed coupled-cluster singles and doubles linear response (CCSD-LR) approach [8] to electroweak quantum chemistry. We report that the ground-state tunneling splitting (for the symmetrical case) is substantially smaller than the parity-violating energy difference. This is the consequence of high interconversion barriers, complex tunneling reaction path and the presence of the three heavy sulphur atoms. Therefore the dynamics of chirality in HSSSH is dominated by de lege symmetry breaking [11] and HSSSH is an ideal candidate for the experiment proposed in [2] to measure ΔpvE, for which the basic experimental capabilities have been demonstrated in our laboratory recently [12]. [1] M. Quack, Fundamental Symmetries and Symmetry Violations from High Resolution Spectroscopy, in Handbook of High-resolution Spectroscopy, edited by F. Merkt and M. Quack, (John Wiley & Sons, Ltd., Chichester, New York, 2011), pp. 659-772. [2] M. Quack, Chem. Phys. Lett. 132, 147 (1986). [3] M. Quack, Angew. Chem. Intl. Ed. (Engl.) 28, 571 (1989). [4] M. Quack, Angew. Chem. Intl. Ed. (Engl.) 41, 4618 (2002). [5] M. Quack, J. Stohner and M. Willeke, Ann. Rev. Phys. Chem. 59, 741 (2008). [6] A. Bakasov, T. K. Ha and M. Quack, J. Chem. Phys. 109, 7263 (1998). [7] R. Berger and M. Quack, J. Chem. Phys. 112, 3148 (2000). [8] Ľ. Horný and M. Quack, Mol. Phys., DOI: 10.1080/00268976.2015.1012131 (2015). [9] B. Fehrensen, D. Luckhaus and M. Quack, Chem. Phys. 338, 90 (2007). [10] A. G. Császár, C. Fábri, T. Szidarovszky, E. Mátyus, T. Furtenbacher and G. Czakó, Phys. Chem. Chem. Phys. 14, 1085 (2012). [11] C. Fábri, Ľ. Horný and M. Quack, to be published. [12] P. Dietiker, E. Miloglyadov, M. Quack, A. Schneider and G. Seyfang, Proc. of the 49th SASP, 152 (2014). QAMTS 2015 – Poster contributions P-7 High Resolution Analysis of the FTIR spectra and quantum dynamics of CHF3 : The 2ν4 (A1 /E) Band Irina Bolotova,1 Oleg Ulenikov,1, 2 Elena Bekhtereva,1, 2 Sieghard Albert,1 Hans Hollenstein,1 and Martin Quack1 1 Physical 2 Physics Chemistry, ETH-Zürich, CH-8093 Zürich, Switzerland Department, Tomsk State University, 634000 Tomsk, Russia CHF3 is a prototype molecule for the study of intramolecular energy flow [1–4]. Despite a long history [1–9] its rotationally resolved infrared spectrum is poorly understood, due to numerous strong interactions. We have reinvestigated the IR spectrum of CHF3 at highest resolution. Here we present the results of reanalysis of the 2ν4 band, located between 2650 and 2850 cm−1 , previously investigated at lower resolution [3, 5]. The band is known as being involved in a Fermi resonance with the stretching fundamental ν1 , which is an essential doorway to intramolecular vibrational redistribution [1–4, 6–9]. The high resolution FTIR spectrum of CHF3 has been measured with the Bruker 125 HR Zürich Prototype spectrometer using a White cell with the optical path length of 19.2 meters at room temperature. As a result of the analysis, transitions up to Jmax = 30 have been assigned for the symmetric component A1 of 2ν4 band, and Jmax = 60 for the 2ν4 (E) band. The new analysis results in a set of effective Hamiltonian parameters, which reproduce the experimental data with an accuracy close to the experimental uncertainties. The results are discussed in relation to further rovibrational interactions and intramolecular energy transfer. We shall also discuss the symmetry of the eigenstates of CHF3 with consideration of inversion tunneling [1 c)]. (Our work is supported by ETHZ, SNF, and ERC). [1] a) S. Albert, K. Keppler Albert, H. Hollenstein, C. Manca-Tanner, and M. Quack Fundamentals of Rotation-Vibration Spectra, Vol. 1, pp. 117-173; b) S. Albert, K. Keppler Albert, and M. Quack High-Resolution Fourier Transform Infrared Spectroscopy, Vol. 2, pp. 965-1019; c) M. Quack Fundamental Symmetries and Symmetry Violations from High-Resolution Spectroscopy, Vol. 1, pp. 659-722 in Handbook of High Resolution Spectroscopy, in Handbook of High Resolution Spectroscopy M. Quack and F. Merkt eds., Wiley Chichester 2011. [2] H. R. Dübal, and M. Quack, Chem. Phys. Lett. 80 439 (1981). [3] H. R. Dübal ,and M. Quack, J. Chem. Phys. 81 3779 (1984). [4] R. Marquardt, M. Quack, J. Stohner and E. Sutcliffe, J. Chem. Soc., Far. Tr. 82 1173 (1986). [5] A. S. Pine, and J. M. Pliva, J. Mol. Spectrosc. 130 431 (1988). [6] J. Segall, R. N. Zare, H. R. Dübal , M. Lewerenz, and M. Quack, J. Chem. Phys. 86 634 (1986). [7] A. Amrein, M. Quack, and U. Schmitt, Mol. Phys. 60 237 (1987). [8] A. Amrein, M. Quack, and U. Schmitt, J. Phys. Chem. 92 5455 (1988). [9] M. Quack, Annu. Rev. Phys. Chem. 41 839 (1990). QAMTS 2015 – Poster contributions P-8 A combined submm wave and synchrotron-based Fourier transform infrared spectroscopic study of meta- and ortho-Dphenol: Probing tunneling switching dynamics Ziqiu Chen,1 Sieghard Albert,1 Robert Prentner,1 and Martin Quack1 1 Physical Chemistry, ETH Zürich, CH-8093 Zürich, Switzerland Tunneling switching is of fundamental interest for certain experiments aiming at detecting parity violation in chiral molecules [1, 2]. A particularly intriguing recent development is the theoretical prediction of prototypical tunneling switching in meta- and ortho-D-phenol (C6H4DOH) as opposed to phenol (C6H5OH) [3] where only tunneling dominates the dynamics: For meta and ortho-D-phenol at low energy, tunneling is completely suppressed due to isotopic substitution, which introduces an asymmetry in the effective potential including zero point vibrational energy in the lowest quasiadiabatic channel. This effectively localizes the molecular wavefunction at either the syn or anti structure of metaand ortho-D-phenol. At higher torsional states of meta- and ortho-D-phenol, tunneling becomes dominant, thus switching the dynamics to a delocalized quantum wavefunction. We have measured and analyzed the rotational spectra of meta- and ortho-D-phenol in the range 60 to 110 GHz, using an experimental setup from [4] which we have improved somewhat, and their rotationally resolved THz and IR spectra in the range 200 to 1000 cm-1 by synchrotron-based FTIR spectroscopy [5]. Here we shall discuss in detail the submm wave spectra of meta- and ortho-D-phenol, which were previously studied only by microwave spectroscopic analyses of the ground vibrational state [6]. We were able to assign and analyze the ground state of the syn and anti isomers of meta- and ortho-D-phenol up to J=35. For meta-D-phenol, assignments of the rotational transitions of the excited torsional states based on the analyzed rovibrational spectra recorded at the synchrotronbased infrared beamline at Swiss Light Source (SLS) [5] will be discussed as well. [1] M. Quack and M. Willeke, J. Phys .Chem. A 110, 3338 (2006). [2] M. Quack, Adv. Chem. Phys. 157, 247 (2014). [3] S. Albert, Ph. Lerch, R. Prentner and M. Quack, Angew. Chem. Int. Ed. 52, 346 (2013). [4] M. Suter and M. Quack, Appl. Opt. 2015 (in press) [5] S. Albert, Ph. Lerch, R. Prentner and M. Quack, 68th International Symposium on Molecular Spectroscopy, Columbus, Ohio, USA, June 17–21, paper TG09 (2013). [6] T. Pedersen, N. W. Larsen and L. Nygaard, J. Mol. Struc. 4, 59-77 (1969). QAMTS 2015 – Poster contributions P-9 Study of large amplitude motions by photoelectron spectroscopy in ethane and 2-butyne radical cations U. Jacovella,1 C. Lauzin,1 B. Gans,2 M. Grütter,3 and F. Merkt1 1 Laboratorium 2 Institut für Physikalische Chemie, ETH Zürich, CH-8093 Zurich, Switzerland des Sciences Moléculaires d’Orsay, Univ Paris-Sud, F-91405 Orsay, France 3 Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, 37077 Göttingen, Germany + The ethane radical cation (H3 C–CH+ 3 ) and the 2-butyne radical cation (H3 C–C≡C–CH3 ) are subject to the Jahn-Teller (JT) and pseudo-Jahn-Teller (PJT) effects. These two cations are structurally similar in that they have two equivalent methyl rotors. However, the internal rotation is expected to be much more hindered in the ethane cation. The experimental information on their energy level structures is so far limited to that contained in lowresolution (∼ 50 cm−1 ) photoelectron spectra [1–3]. We present high-resolution (∼ 0.4 cm−1 ) pulsed-field-ionization zero-kinetic-energy (PFIZEKE) photoelectron spectra of ethane and 2-butyne in the region of the origin band and of transitions to low-lying vibrational levels of the cations with partially resolved rotational structure. From these spectra, we have derived new information on the cations, which reveals a completely different behaviour, particularly concerning the strength of the JT, PJT and spin-orbit coupling and the role of internal rotation. The rotational structure observed in the photoelectron spectrum of 2-butyne indicates a weak JT effect and an observable spin-orbit splitting of ∼ 10.5 cm−1 between the two components E3/2 and E1/2 of of the X̃ + 2 E2(d) ground state, which is in agreement with the results of recent ab-initio calculations [4]. It also reveals spectral patterns that we attribute to an almost free internal rotation. The vibrational level structure observed in the photoelectron spectrum of ethane shows much stronger JT and PJT effects as has been predicted in Ref. 5, which completely quench the spin-orbit coupling. In the vicinity of the ionization threshold, several isomers resulting from the ionization of the eg and a1g orbitals have been predicted ab initio [6, 7]. The rotational structure observed in the photoelectron spectrum provides information on the structure of those isomers. [1] P. Carlier, J.E. Dubois, P. Masclet and G. Mouvier, J. Electron Spectrosc., 7, (1975) 55-67. [2] H. Xu, U. Jacovella, B. Ruscic, S.T. Pratt and R.R. Lucchese, J. Chem. Phys., 136, (2012) 154303. [3] J. W. Rabalais and A. Katrib, Mol. Phys., 27, (1974) 923. [4] S. Knecht and M. Reiher, ETH Zürich, private communication (2014). [5] T. S. Venkatesan and S. Mahapatra, J. Chem. Phys., 123, (2005) 114308. [6] A. Ioffe and S. Shaik, J. Chem. Soc., Perkin Trans. 2, 8, (1993) 1461-1473. [7] H. M. Sulzbach, D. Graham, J. C. Stephens and H. F. Schaefer III, Acta. Chem. Scand, 51, (1997) 547-555. P-10 QAMTS 2015 – Poster contributions High resolution infrared spectroscopy and theory of parity violation and tunneling for dithiine as a candidate for measuring the parity violating energy difference between enantiomers of chiral molecules S. Albert, I. Bolotova, Z. Chen, C. Fabri, L. Horny, M. Quack, G. Seyfang and D. Zindel 1 Physical Chemistry, ETH Zurich, CH-8093 Zurich, Switzerland, 2 Swiss Light Source, PSI, CH-5232 Villigen, Switzerland In the framework of ordinary “electromagnetic” quantum theory the ground states of the enantiomers of chiral molecules are energetically equivalent. However, with the electroweak quantum chemistry and parity violation, one predicts a small “parity violating” difference DPVE on the order of 100 aeV, typically, depending on the molecule, corresponding to a reaction enthalpy of stereomutation of about 10-11 J mol-1 [1,2]. So far, this effect has never been observed experimentally. In our paper, we report exploratory spectroscopy and theory in view of a possible use of the chiral C2-symmetric molecule dithiine (C4H4S2) for detecting molecular parity violation using a current experimental setup in our laboratory [3]. Using high resolution FTIR spectroscopy [4] we were able to provide a first rovibrational analysis of two bands, one centered at 623.3121 cm-1 consisting of c-type transitions and the second centered at 1308.8724 cm-1 consisting of a-type transitions. The assignments have been verified by combination differences. In parallel we calculated parity violating potentials using our recent coupled cluster approach [5] and tunneling using our quasiadiabatic channel reaction path Hamiltonian approach [6] . The implication of our results for the study of molecular parity violation will be discussed. [1] M. Quack, Fundamental symmetries and symmetry violations from high resolution spectroscopy, in Handbook of High-Resolution Spectroscopy, Vol. 1, (Eds. M Quack and F Merkt), Wiley, Chichester (2011), 965-1021. [2] M. Quack, Angew. Chem.-Int. Edit. Engl. 1989, 28, 571-586. [3] P. Dietiker, E. Milogyadov, M. Quack, A. Schneider and G. Seyfang, in Proceedings of the 19th Symposium on Atomic, Cluster and Surface Physics (SASP 2014), University center Obergurgl, Austria, 8th to 14th February 2014, edited by D. Stock, R. Wester and R. Scheier (Innsbruck University Press, Innsbruck, 2014), pp. 226–229. ISBN: 978–3–902936–26–4. [4] S. Albert, K. K. Albert and M. Quack, High Resolution Fourier Transform Infrared Spectroscopy, in Handbook of High-Resolution Spectroscopy, Vol. 2, (Eds. M Quack and F Merkt), Wiley, Chichester (2011), 965-1021. S. Albert and M. Quack, ChemPhysChem., 8, 1271 – 1281 (2007). [5] L. Horny and M. Quack, Mol. Phys. (2015) in press. [6] B. Fehrensen, D. Luckhaus, M. Quack, Chemical Physics 2007, 338, 90-105. List of authors Albert, Sieghard, L-20, P-7, P-8, P-10 Allemann, Rudolf K., L-25 Allen, Wesley D., L-5 Álvarez-Barcia, Sonia, L-40 Anovitz, L.M., L-4 Aquilanti, Vincenzo, L-37 Aquino, Adelia, L-14 Asselin, P., L-22 Bačić, Zlatko, L-3 Baouche, Saoud, L-21 Batel, Michael, L-13 Baykusheva, D., L-36 Bekhtereva, Elena, P-7 Berger, Y., L-22 Bodi, Andras, L-10 Bolotova, Irina, P-7, P-10 Borden, Weston Thatcher, L-28 Bravaya, Ksenia B., L-10 Bredtmann, Timm, L-29 Briant, M., L-9 Cavalli, Simonetta, L-37 Chaabouni, Henda, L-21 Chapovsky, P.L., L-15 Chen, Ziqiu, L-20, P-8, P-10 Chevalier, M., L-9 Congiu, Emanuele, L-21 Costa, Paolo, L-8 Crépin, C., L-9 Császár, Attila G., L-5 De Fazio, Dario, L-37 Dietiker, Peter, L-41 Dong, Wei, L-17 Dulieu, Francois, L-21 Dulitz, Katrin, L-23 Eckert, Juergen, L-32 Ehlers, G., L-4 Ernst, Matthias, L-13, P-4 Ernst, Wolfgang E., L-35 Ertelt, Melanie, L-8, L-28 Fábri, Csaba, L-42, P-6, P-10 Field, Robert W., L-34 Firmino, Thiago, L-17 Fleming, Donald G., L-2 Gans, B., P-9 Garrett, Bruce C., L-2 Gatti, Fabien, L-17 Georges, R., L-22 Ghosh, Supriya, L-18 Gonzalez, Megan, L-14 Goubet, M., L-22 Goumans, T. P. M. (Fedor), L-40 Grütter, M., P-9 Gutierrez-Quintanilla, A., L-9 Henkel, Stefan, L-8, L-28, P-2 Hollenstein, Hans, P-7 Hollenstein, U., L-23, P-5 Horný, Ľuboš, L-24, L-36, P-6, P-10 Hrovat, David A., L-28 Huet, T. R., L-22 Inui, Hiroshi, L-38 Jacovella, U., P-9 Jäger, Wolfgang, L-18 Jähnig, Fabian, L-13, P-4 Karandashev, Konstantin, L-26 Kästner, Johannes, L-40 Kohen, Amnon, L-27 QAMTS 2015 – List of authors Kolesnikov, A.I., L-4 Kozuch, Sebastian, L-11 Kraus, P. M., L-36 Krzystyniak, M., L-33 Küpper, Jochen, L-6, P-3 Kyuberis, Alexandra A., L-34 Lauzin, C., P-9 Lerch, Philippe, L-20 Leutwyler, Samuel, L-16 Levitt, Malcolm H., L-19 Li, Si-Dian, L-29 Limbach, Hans-Heinrich, L-12 Loveridge, E. Joel, L-25 Luk, Louis Y. P., L-25 Mamontov, E., L-4 Manz, Jörn, L-29 Marquardt, Roberto, L-17, L-42 McAfee, Jason, L-14 McMahon, Robert J., L-38 Meier, Beat H., L-13, P-4 Mellau, Georg Ch., L-34 Merkt, F., L-23, P-5, P-9 Mestdagh, J.-M, L-9 Mielke, Steven L., L-2 Milogyadov, Eduard, L-41 Minissale, Marco, L-21 Momose, Takamasa, L-1 Nielsen, Anders B., L-13, P-4 Ottiger, Philipp, L-16 Parrinello, Michele, L-31 Pham, Tony, L-32 Pirali, O., L-22 Podlesnyak, A., L-4 Poirier, Bill, L-14 Poisson, L., L-9 Polyansky, Oleg L., L-34 Prentner, Robert, P-8 Prisk, T.R., L-4 Quack, Martin, L-20, L-24, L-41, L-42, P-6–P-8, P-10 Reiter, G.F., L-4 Reva, Igor, L-43 Rommel, Judith B., L-40 Roth, Ch., L-36 Rudert, Rainer, P-1 Sander, Wolfram, L-8, L-28, P-2 Schmutz, H., P-5 Schneider, Andreas, L-41 Schnitzler, Elijah G., L-18 Schreiner, Peter R., L-5 Seel, A., L-4 Seyfang, Georg, L-41, P-10 Signorell, Ruth, L-10 Soulard, P., L-22 Stare, Jernej, L-39 Thomas, Javix, L-18 Tian, Wen-Juan, L-29 Tomaselli, Marco, L-13 Trippel, Sebastian H., P-3 Trosien, Iris, L-8 Truhlar, Donald G., L-2 Ulenikov, Oleg, P-7 Vaníček, Jiří, L-26 Vasilatou, Konstantina, L-23 Vogt, Jürgen, P-1 Vogt, Natalja, P-1 Wales, David J., L-30 Waluk, Jacek, L-7 Wiese, Joss, P-3 Wörner, H. J., L-36 Wu, Yan-Bo, L-29 Xu, Yunjie, L-18 Xue, Zhifeng, L-16 Yang, Yonggang, L-29 Yoder, Bruce L., L-10 Zenchyzen, Brandi L. M., L-18 Zhai, Hua-Jin, L-29 Zhang, Xue, L-28 Zindel, D., P-10 Zobov, Nikolai, L-34 List of participants Albert, Sieghard, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Allemann, Rudolf K., Cardiff University, School of Chemistry, Cardiff, UK, [email protected] Aquilanti, Vincenzo, Università di Perugia, Dipartimento di Chimica, Biologia e Biotecnologie, Perugia, Italy, [email protected] Asselin, Pierre, Université Pierre et Marie Curie, CNRS/UPMC, Paris, France, [email protected] Bacic, Zlatko, New York University, Department of Chemistry, New York, USA, [email protected] Bolotova, Irina, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Borden, Sheila, University of North Texas, Department of Chemistry, Denton, Texas, USA, [email protected] Borden, Weston Thatcher, University of North Texas, Department of Chemistry and the Center for Advanced, Scientific Computing and Modeling, Denton, Texas, USA, [email protected] Chapovsky, Pavel, The Russian Academy of Sciences, Novosibirsk State University, Institute of Automation and Electrometry, Novosibirsk, Russia, [email protected] Chen, Ziqiu, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Csaszar, Attila Geza, Eotvos University, Institute of Chemistry, Budapest, Hungary, [email protected] Dulieu, Francois, Cergy Pontoise Univesity, LERMA, Cergy Pontoise, France, [email protected] Dulitz, Katrin, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Eckert, Juergen, University of South Florida, Santa Fe, USA, [email protected] Ernst, Wolfgang E., Graz University of Technology, Institute of Experimental Physics, Graz, Austria, [email protected] Fábri, Csaba, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Garrett, Bruce Campbell, Pacific Northwest National Laboratory, Richland, USA, [email protected] QAMTS 2015 – List of participants Henkel, Stefan, Ruhr-Universität Bochum, Lehrstuhl für organische Chemie II, Bochum, Germany, [email protected] Hollenstein, Urs, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Horny, Lubos, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Jacovella, Ugo, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Jaeger, Wolfgang, University of Alberta, Department of Chemistry, Edmonton, Canada, [email protected] Jähnig, Fabian, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Kästner, Johannes, University of Stuttgart, Institut für theoretische Chemie, Stuttgart, Germany, [email protected] Kohen, Amnon, University of Iowa, Department of Chemistry, Iowa City, USA, [email protected] Kolesnikov, Alexander Ivanovich, Oak Ridge National Laboratory, Oak Ridge, USA, [email protected] Kozuch, Sebastian, Ben-Gurion University of the Negev, Department of Chemistry, Be’er-Sheva, Israel, [email protected] Krzystyniak, Maciej, Rutherford Appleton Laboratory, ISIS Neutron and Muon Source, Didcot, UK, [email protected] Küpper, Jochen, University of Hamburg, Centre for Free-Electron laser Science, DESY, Hamburg, Germany, [email protected] Leutwyler, Samuel, Universität Bern, Departement für Chemie und Biochemie, Bern, Switzerland, [email protected] Levitt, Malcolm, Southampton University, Chemistry, Southampton, UK, [email protected] Limbach, Hans Heinrich, Freie Universität Berlin, Institut für Chemie und Biochemie, Berlin, Germany, [email protected] Manz, Jörn, Shanxi University, State Key Laboratory of Quantum Optics and Quantum Optics Devices, and Freie Universität Berlin, Institut für Chemie und Biochemie, Taiyuan, China, [email protected] Marquardt, Roberto, Université de Strasbourg, Laboratoire de Chimie Quantique, Strasbourg, France, [email protected] McMahon, Robert J, University of Wisconsin, Department of Chemistry, Madison, USA, [email protected] Meier, Beat H., ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Mellau, Georg, Justus-Liebig-Universität Gießen, Physikalisch-Chemisches Institut, Gießen, Germany, [email protected] Merkt, Frédéric, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] QAMTS 2015 – List of participants Mestdagh, Jean-Michel, CEA/DSM/IRAMIS/LIDyL - CNRS URA 2453, Laboratoire Francis Perrin, Gif-sur-Yvette CEDEX, France, [email protected] Miloglyadov, Eduard, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Momose, Takamasa, University of British Columbia, Department of Chemistry, Vancouver, Canada, [email protected] Parrinello, Michele, ETH Zürich and USI Lugano, Departement Chemie und Angewandte Biowissenschaften, Lugano, Switzerland, [email protected] Poirier, Lionel William, Texas Tech University, Lubbock, USA, [email protected] Quack, Martin, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Reva, Igor, University of Coimbra, Department of Chemistry, Coimbra, Portugal, [email protected] Sander, Wolfram, Ruhr-Universität Bochum, Bochum, Germany, [email protected] Seyfang, Georg, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Stare, Jernej, National Institute of Chemistry, Ljubljana, Slovenia, [email protected] Vanicek, Jiri, EPFL Lausanne, Lausanne, Switzerland, [email protected] Vogt, Jürgen, Universität Ulm, Chemieinformationssysteme, Ulm, Germany, [email protected] Vogt, Natalja, Universität Ulm, Chemieinformationssysteme, Ulm, Germany, [email protected] Wales, David, Cambridge, University Chemical Labs, Cambridge, UK, [email protected] Waluk, Jacek, Polish Academy of Sciences, Warsaw, Poland, [email protected] Willeke, Martin, ETH Zürich, Department of Materials, Zürich, Switzerland, [email protected] Wörner, Hans Jakob, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Yoder, Bruce L, ETH Zürich, Laboratorium für Physikalische Chemie, Zürich, Switzerland, [email protected] Physical Chemistry Chemical Physics (PCCP) Highest quality research in physical chemistry, chemical physics and biophysical chemistry • Renowned for fast publication • Not-for-profit publication • Co-owned by 19 National Societies • Efficient, rigorous and fair peer review • Impact Factor 4.20 Submit your best research today: PCCPjournal @PCCP www.rsc.org/pccp Registered charity number: 207890 Molecular Physics Molecular Physics is a well-established international journal publishing original high quality papers in chemical physics and physical chemistry. The journal covers all experimental and theoretical aspects of molecular science, from electronic structure, molecular dynamics, spectroscopy and reaction kinetics to condensed matter, surface science, and statistical mechanics of simple and complex fluids. Contributions include full papers, preliminary communications, research notes and invited topical review articles. research notes and invited topical review and new view articles. Visit the Molecular Physics homepage for the latest news and offers from the journal, including: Virtual Issues The Editors have selected their favourite articles from the previous 2 volumes of Molecular Physics and you can view them for free online. New Views and Topical Views To showcase the exciting content published in Molecular Physics, articles in both the New Views and Topical articles in both the New Views and Topical Reviews series are available to read online with free access available to read online with free access for the first 2 months after publication in an issue. Indexed in Thomson Reuters Web of Science® www.chemistryarena.com Visit the Chemistry Arena for the latest news and offers from our books and journals including: w Key research collections wEditor’s picks wConference information wSpecial issues wOpen access wBook of the month Find out more at: www.chemistryarena.com Longuet-Higgins Early Career Researcher Prize Every year the Editors of Molecular Physics award the LonguetHiggins Early Career Researcher Prize of US$1000 to a talented author who is judged to have made a significant contribution to a top quality paper published in the journal the previous year. Register your email to receive information on journals and books in your subject area www.tandfonline.com/eUpdates bit.ly/MolecularPhysics
