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Quantum Chemistry for Excited States of Large Molecules:
from Organic Dyes to Light Harvesting Complexes
A. Dreuw
Institute of Physical and Theoretical Chemistry, Johann Wolfgang Goethe-University,
Max von Laue-Str. 7 60438 Frankfurt/Main, Germany
(e-mail: [email protected])
In my talk, the current status of existing methods for the computation of electronic
excited states of large and medium-sized molecules will be discussed. In particular
the potential of time-dependent density functional theory (TDDFT) and its failure for
charge-transfer excited states will be highlighted [1]. Here, the origin of the problem
as well as possible correction schemes will be described [2,3]. The development of an
additive long-range corrected xc-potential and its current progress is summarized.
In addition, the algebraic diagrammatic construction scheme of second order
(ADC(2)) will be introduced which allows for the physically correct calculation of
excited states with single and double excitation character as well as of charge-transfer
excited states [4]. Recent developments, e.g. the derivation and implementation of an
unrestricted UADC scheme as well as of a local ADC(2) version will be summarized
[5]. Furthermore, our implementation of the intermediate-state-representation of the
dipole operator allows for the calculation of excited-state absorption and resonant
two-photon absorption spectra. Accompanying applications of these approaches to
medium-sized molecules will demonstrate their applicability to photochemical and
photobiological questions.
[1] A. Dreuw and M. Head-Gordon, Chem. Rev. (2005) 105, 4009.
[2] A. Dreuw, Chem. Phys. Chem. (2006) 7, 2259.
[3] A. Dreuw and M. Head-Gordon, J. Am. Chem. Soc. (2004) 126, 4007.
[4] J. H. Starcke, M. Wormit, J. Schirmer and A. Dreuw, Chem. Phys. (2006) 329, 39.
[5] J. H. Starcke, M. Wormit and A. Dreuw, J. Chem. Phys. (2009) 130, 024104.