Description of ground and excited electronic states by ensemble density functional method with extended active space.

Citation data:

The Journal of chemical physics, ISSN: 1089-7690, Vol: 147, Issue: 6, Page: 064104

Publication Year:
2017
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Repository URL:
http://scholarworks.unist.ac.kr/handle/201301/22618
PMID:
28810777
DOI:
10.1063/1.4996873
Author(s):
Filatov, Michael; Martínez, Todd J.; Kim, Kwang S.
Publisher(s):
AIP Publishing; AMER INST PHYSICS
Tags:
Physics and Astronomy; Chemistry
article description
An extended variant of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, the REKS(4,4) method, designed to describe the ground electronic states of strongly multireference systems is modified to enable calculation of excited states within the time-independent variational formalism. The new method, the state-interaction state-averaged REKS(4,4), i.e., SI-SA-REKS(4,4), is capable of describing several excited states of a molecule involving double bond cleavage, polyradical character, or multiple chromophoric units. We demonstrate that the new method correctly describes the ground and the lowest singlet excited states of a molecule (ethylene) undergoing double bond cleavage. The applicability of the new method for excitonic states is illustrated with π stacked ethylene and tetracene dimers. We conclude that the new method can describe a wide range of multireference phenomena.