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

Abstract

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:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1390629
Alternate Identifier(s):
OSTI ID: 1374479
Grant/Contract Number:  
AC02-76SF00515
Resource 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)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

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., 2017. 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. Mon . "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}
}

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