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Title: Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs

Abstract

Here, the spin-restricted ensemble-referenced Kohn-Sham (REKS) method is based on an ensemble representation of the density and is capable of correctly describing the non-dynamic electron correlation stemming from (near-)degeneracy of several electronic configurations. The existing REKS methodology describes systems with two electrons in two fractionally occupied orbitals. In this work, the REKS methodology is extended to treat systems with four fractionally occupied orbitals accommodating four electrons and self-consistent implementation of the REKS(4,4) method with simultaneous optimization of the orbitals and their fractional occupation numbers is reported. The new method is applied to a number of molecular systems where simultaneous dissociation of several chemical bonds takes place, as well as to the singlet ground states of organic tetraradicals 2,4-didehydrometaxylylene and 1,4,6,9-spiro[4.4]nonatetrayl.

Authors:
 [1]; ORCiD logo [2];  [1]; ORCiD logo [2]
  1. Ulsan National Institute of Science and Technology (UNIST), Ulsan (South Korea)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1361133
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 24; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Filatov, Michael, Liu, Fang, Kim, Kwang S., and Martínez, Todd J. Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs. United States: N. p., 2016. Web. doi:10.1063/1.4972174.
Filatov, Michael, Liu, Fang, Kim, Kwang S., & Martínez, Todd J. Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs. United States. doi:10.1063/1.4972174.
Filatov, Michael, Liu, Fang, Kim, Kwang S., and Martínez, Todd J. Thu . "Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs". United States. doi:10.1063/1.4972174. https://www.osti.gov/servlets/purl/1361133.
@article{osti_1361133,
title = {Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs},
author = {Filatov, Michael and Liu, Fang and Kim, Kwang S. and Martínez, Todd J.},
abstractNote = {Here, the spin-restricted ensemble-referenced Kohn-Sham (REKS) method is based on an ensemble representation of the density and is capable of correctly describing the non-dynamic electron correlation stemming from (near-)degeneracy of several electronic configurations. The existing REKS methodology describes systems with two electrons in two fractionally occupied orbitals. In this work, the REKS methodology is extended to treat systems with four fractionally occupied orbitals accommodating four electrons and self-consistent implementation of the REKS(4,4) method with simultaneous optimization of the orbitals and their fractional occupation numbers is reported. The new method is applied to a number of molecular systems where simultaneous dissociation of several chemical bonds takes place, as well as to the singlet ground states of organic tetraradicals 2,4-didehydrometaxylylene and 1,4,6,9-spiro[4.4]nonatetrayl.},
doi = {10.1063/1.4972174},
journal = {Journal of Chemical Physics},
number = 24,
volume = 145,
place = {United States},
year = {2016},
month = {12}
}

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