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

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 newmethod 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.
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Ulsan National Inst. of Science and Technology (Korea, Republic of)
  2. Stanford Univ., CA (United States)
Publication Date:
Grant/Contract Number:
AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 6; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
OSTI Identifier:
1390629
Alternate Identifier(s):
OSTI ID: 1374479

Filatov, Michael, Martínez, Todd J., and Kim, Kwang S.. Description of ground and excited electronic states by ensemble density functional method with extended active space. United States: N. p., Web. doi:10.1063/1.4996873.
Filatov, Michael, Martínez, Todd J., & Kim, Kwang S.. Description of ground and excited electronic states by ensemble density functional method with extended active space. United States. doi:10.1063/1.4996873.
Filatov, Michael, Martínez, Todd J., and Kim, Kwang S.. 2017. "Description of ground and excited electronic states by ensemble density functional method with extended active space". United States. doi:10.1063/1.4996873. https://www.osti.gov/servlets/purl/1390629.
@article{osti_1390629,
title = {Description of ground and excited electronic states by ensemble density functional method with extended active space},
author = {Filatov, Michael and Martínez, Todd J. and Kim, Kwang S.},
abstractNote = {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 newmethod 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.},
doi = {10.1063/1.4996873},
journal = {Journal of Chemical Physics},
number = 6,
volume = 147,
place = {United States},
year = {2017},
month = {8}
}