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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4972174· OSTI ID:1361133
 [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)
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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.

Research Organization:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1361133
Journal Information:
Journal of Chemical Physics, Vol. 145, Issue 24; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

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Cited By (8)

Analytical derivatives of the individual state energies in ensemble density functional theory method. I. General formalism journal July 2017
Description of ground and excited electronic states by ensemble density functional method with extended active space journal August 2017
Communication: Density functional theory model for multi-reference systems based on the exact-exchange hole normalization journal March 2018
Ground and excited energy levels can be extracted exactly from a single ensemble density-functional theory calculation journal March 2019
Non-adiabatic molecular dynamics with ΔSCF excited states journal November 2018
Exploring weight-dependent density-functional approximations for ensembles in the Hubbard dimer journal July 2018
Exploring weight-dependent density-functional approximations for ensembles in the Hubbard dimer text January 2018
Ground and excited energy levels can be extracted exactly from a single ensemble density-functional theory calculation text January 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY