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Using on-top pair density for construction of correlation functionals for multideterminant wave functions

Gusarov, Sergey LU ; Malmqvist, Per-Åke LU and Lindh, Roland (2004) In Molecular Physics 102(21-22). p.2207-2216
Abstract
The value of the two-particle density function at coalescence is frequently used as an additional variable for formulating approximate exchange-correlation or correlation functionals. Here, its applications as one of the key variables for the construction of new DFT (preferably multi-determinant) functionals is investigated. The basic formalism is presented and it is shown that this replacement avoids some difficulty to construct a Fock matrix in a ROKS (restricted open-shell Kohn-Sham) method and also to reduce the 'double counting' of correlation energy in CASDFT (complete active space density functional theory) calculations. Calculations of excitation energies for transition metals and dissociation curves for diatomic molecules are... (More)
The value of the two-particle density function at coalescence is frequently used as an additional variable for formulating approximate exchange-correlation or correlation functionals. Here, its applications as one of the key variables for the construction of new DFT (preferably multi-determinant) functionals is investigated. The basic formalism is presented and it is shown that this replacement avoids some difficulty to construct a Fock matrix in a ROKS (restricted open-shell Kohn-Sham) method and also to reduce the 'double counting' of correlation energy in CASDFT (complete active space density functional theory) calculations. Calculations of excitation energies for transition metals and dissociation curves for diatomic molecules are presented as an example. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Molecular Physics
volume
102
issue
21-22
pages
2207 - 2216
publisher
Taylor & Francis
external identifiers
  • wos:000225979200006
  • scopus:10844226716
ISSN
1362-3028
DOI
10.1080/00268970410001734297
language
English
LU publication?
yes
id
dfac1af3-c1eb-442c-be6e-643d6aa3658f (old id 141448)
date added to LUP
2007-07-03 11:46:57
date last changed
2017-03-26 03:39:25
@article{dfac1af3-c1eb-442c-be6e-643d6aa3658f,
  abstract     = {The value of the two-particle density function at coalescence is frequently used as an additional variable for formulating approximate exchange-correlation or correlation functionals. Here, its applications as one of the key variables for the construction of new DFT (preferably multi-determinant) functionals is investigated. The basic formalism is presented and it is shown that this replacement avoids some difficulty to construct a Fock matrix in a ROKS (restricted open-shell Kohn-Sham) method and also to reduce the 'double counting' of correlation energy in CASDFT (complete active space density functional theory) calculations. Calculations of excitation energies for transition metals and dissociation curves for diatomic molecules are presented as an example.},
  author       = {Gusarov, Sergey and Malmqvist, Per-Åke and Lindh, Roland},
  issn         = {1362-3028},
  language     = {eng},
  number       = {21-22},
  pages        = {2207--2216},
  publisher    = {Taylor & Francis},
  series       = {Molecular Physics},
  title        = {Using on-top pair density for construction of correlation functionals for multideterminant wave functions},
  url          = {http://dx.doi.org/10.1080/00268970410001734297},
  volume       = {102},
  year         = {2004},
}