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Excited State Studies of Polyacenes Using the All-Order Constricted Variational Density Functional Theory with Orbital Relaxation

For the polyacenes series from naphthalene to hexacene, we present the vertical singlet excitation energies 1 1La and 1 1Lb, as well as the first triplet excitation energies obtained by the all-order constricted variational density functional theory with orbital relaxation (R-CV(∞)-DFT). R-CV(∞)-DFT...

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Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2015-10, Vol.119 (42), p.10575-10581
Main Authors: Senn, Florian, Krykunov, Mykhaylo
Format: Article
Language:English
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Summary:For the polyacenes series from naphthalene to hexacene, we present the vertical singlet excitation energies 1 1La and 1 1Lb, as well as the first triplet excitation energies obtained by the all-order constricted variational density functional theory with orbital relaxation (R-CV(∞)-DFT). R-CV(∞)-DFT is a further development of variational density functional theory (CV(∞)-DFT), which has already been successfully applied for the calculation of the vertical singlet excitation energies 1La and 1Lb for polyacenes, and we show that one obtains consistent excitation energies using the local density approximation as a functional for singlet as well as for triplet excitations when going beyond the linear response theory. Furthermore, we apply self-consistent field density functional theory (ΔSCF-DFT) and compare the obtained excitation energies for the first triplet excitations T1, where, due to the character of the transition, ΔSCF-DFT and R-CV(∞)-DFT become numerically equivalent, and for the singlet excitations 1 1La and 1 1Lb, where the two methods differ.
ISSN:1089-5639
1520-5215
DOI:10.1021/acs.jpca.5b07075