Direct determination of exciton couplings from subsystem time-dependent density-functional theory within the Tamm-Dancoff approximation.
In subsystem time-dependent density functional theory (TDDFT) [J. Neugebauer, J. Chem. Phys. 126, 134116 (2007)] localized excitations are used to calculate delocalized excitations in large chromophore aggregates. We have extended this formalism to allow for the Tamm-Dancoff approximation (TDA). The resulting response equations have a form similar to a perturbative configuration interaction singles (CIS) approach. Thus, the inter-subsystem matrix elements in subsystem TDA can, in contrast to the full subsystem-TDDFT case, directly be interpreted as exciton coupling matrix elements. Here, we present the underlying theory of subsystem TDDFT within the TDA as well as first applications. Since for some classes of pigments, such as linear polyenes and carotenoids, TDA has been reported to perform better than full TDDFT, we also report applications of this formalism to exciton couplings in dimers of such pigments and in mixed bacteriochlorophyll-carotenoid systems. The improved description of the exciton couplings can be traced back to a more balanced description of the involved local excitations.
Theoretische Organische Chemie, Organisch-Chemisches Institut der Westfälischen Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster, Germany.
Carolin
C
König
Nicolas
N
Schlüter
Johannes
J
Neugebauer
D001429:Bacteriochlorophylls / Q000737:chemistry; D002338:Carotenoids / Q000737:chemistry; D011789:Quantum Theory; D013997:Time Factors
D001429:Bacteriochlorophylls; D002338:Carotenoids