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.
Skip Nav Destination
Article navigation
28 December 2016
Research Article|
December 22 2016
Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs
Michael Filatov;
Michael Filatov
a)
1Department of Chemistry, School of Natural Sciences,
Ulsan National Institute of Science and Technology (UNIST)
, Ulsan 689-798, South Korea
Search for other works by this author on:
Fang Liu
;
Fang Liu
2
Department of Chemistry and The PULSE Institute
, Stanford University, Stanford, California 94305, USA and SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
Search for other works by this author on:
Kwang S. Kim;
Kwang S. Kim
1Department of Chemistry, School of Natural Sciences,
Ulsan National Institute of Science and Technology (UNIST)
, Ulsan 689-798, South Korea
Search for other works by this author on:
Todd J. Martínez
Todd J. Martínez
2
Department of Chemistry and The PULSE Institute
, Stanford University, Stanford, California 94305, USA and SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
Search for other works by this author on:
a)
Electronic mail: mike.filatov@gmail.com
J. Chem. Phys. 145, 244104 (2016)
Article history
Received:
October 19 2016
Accepted:
December 01 2016
Citation
Michael Filatov, Fang Liu, Kwang S. Kim, Todd J. Martínez; Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs. J. Chem. Phys. 28 December 2016; 145 (24): 244104. https://doi.org/10.1063/1.4972174
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Sign in via your Institution
Sign in via your InstitutionPay-Per-View Access
$40.00
Citing articles via
Related Content
Double spin-flip approach within equation-of-motion coupled cluster and configuration interaction formalisms: Theory, implementation, and examples
J. Chem. Phys. (January 2009)
Description of ground and excited electronic states by ensemble density functional method with extended active space
J. Chem. Phys. (August 2017)
What to do about unpaired electrons? A hydrocarbon hexaradical with three Closs diradicals linked by 1,3,5-trimethylbenzene as ferromagnetic coupler
J. Chem. Phys. (September 2002)