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Transcript
Chiroptics2017
5 – 8 April 2017 in Munich, Germany
Parity Violation in Chiral Molecules: From Theory towards
Spectroscopic Experiment and the Evolution of Biomolecular
Homochirality Martin Quack
ETH Zürich, Physical Chemistry, CH-8093 Zürich, Switzerland
e-mail [email protected]
We shall start with an introductory discussion of three fundamental questions relating
physics to molecular quantum dynamics and stereochemistry.
(i)
To what extent are the fundamental symmetries and conservation laws of
physics and their violations reflected in molecular quantum dynamics and
spectroscopy, in general?
(ii)
How important is parity violation for the quantum dynamics and spectroscopy of
chiral molecules, in particular?
(iii)
How important is parity violation for biomolecular homochirality, i.e. the quasi
exclusive preference of L-amino acids and D-sugars in the biopolymers of life
(proteins and DNA)?
The observation of biomolecular homochirality can be considered as a quasi-fossil of
the evolution of life 1-2, the interpretation of which has been an open question for more
than a century, with numerous related hypotheses, but no definitive answers. We shall
briefly discuss the current status and the relation to the other two questions.
The discovery of parity violation led to important developments of physics in the 20th
century and is understood within the standard model of particle physics, SMPP. For
molecular stereochemistry it leads to the surprising prediction of a small energy
difference D of the ground state energies of the enantiomers of chiral molecules,
corresponding to a small reaction enthalpy for the stereomutation between the R and
S enantiomers 3.This reaction enthalpy would be exactly zero by symmetry with exact
parity conservation. Theory predicts D to be in the sub-femto eV range, typically,
depending on the molecule (about D = 100 aeV for ClSSCl or CHFClBr,
corresponding to a reaction enthalpy of about 10 pJ/mol). We have outlined three
decades ago, how this small energy difference D might by measured by spectroscopic
experiment 4, and recent progress indicates that experiment might be successful in
the near future
5-9
. We shall discuss the current status of our experiments including
Chiroptics2017
5 – 8 April 2017 in Munich, Germany
alternatives pursued in other groups and the possible consequences for our
understanding of molecular and biomolecular chirality.For background reading see 1-9.
1. Quack, M., On Biomolecular Homochirality as a Quasi-Fossil of the Evolution of
Life. Adv. Chem. Phys. 2015, 157, 249-290.
2. Quack, M., Die Spiegelsymmetrie des Raumes und die Chiralität in Chemie,
Physik, und in der biologischen Evolution. Nova Acta Leopoldina NF 2016, 412,
119-166.
3. Quack, M., Fundamental Symmetries and Symmetry Violations from High
Resolution Spectroscopy. In Handbook of High Resolution Spectroscopy, Quack, M.;
Merkt, F., Eds. Wiley: Chichester, New York, 2011; Vol. 1, pp 659-722.
4. Quack, M., On the measurement of the parity violating energy difference between
enantiomers. Chem. Phys. Lett. 1986, 132 (2), 147-153.
5. Dietiker, P.; Miloglyadov, E.; Quack, M.; Schneider, A.; Seyfang, G., Infrared laser
induced population transfer and parity selection in 14NH3: A proof of principle
experiment towards detecting parity violation in chiral molecules. J. Chem. Phys. 2015,
143 (24), 244305.
6. Prentner, R.; Quack, M.; Stohner, J.; Willeke, M., Wavepacket Dynamics of the
Axially Chiral Molecule Cl-O-O-Cl under Coherent Radiative Excitation and Including
Electroweak Parity Violation. J. Phys. Chem. A 2015, 119 (51), 12805–12822.
7. Fábri, C.; Horný, Ľ.; Quack, M., Tunneling and Parity Violation in Trisulfane
(HSSSH): An Almost Ideal Molecule for Detecting Parity Violation in Chiral Molecules.
ChemPhysChem 2015, 16 (17), 3584–3589.
8. Albert, S.; Bolotova, I.; Chen, Z.; Fábri, C.; Horný, L.; Quack, M.; Seyfang, G.;
Zindel, D., High resolution GHz and THz (FTIR) spectroscopy and theory of parity
violation and tunneling for 1,2-dithiine (C4H4S2) as a candidate for measuring the
parity violating energy difference between enantiomers of chiral molecules. Phys.
Chem. Chem. Phys. 2016, 18 (31), 21976-21993.
9. Albert, S.; Arn, F.; Bolotova, I.; Chen, Z.; Fábri, C.; Grassi, G.; Lerch, P.; Quack,
M.; Seyfang, G.; Wokaun, A.; Zindel, D., Synchrotron-Based Highest Resolution
Terahertz Spectroscopy of 1,2-Dithiine (C4H4S2): A Candidate for Measuring the Parity
Violating Energy Difference between Enantiomers of Chiral Molecules. J. Phys. Chem.
Lett. 2016, 7, 3847-3853.