We propose a multiconfiguration density functional combining a short-range density functional approximation with a novel long-range correction for dynamic correlation effects. The correction is derived from the adiabatic connection formalism so that the resulting functional requires access only to one- and two-electron reduced density matrices of the system. In practice, the functional is formulated for wavefunctions of the complete active space (CAS) type and the short-range density functional part is made dependent on the on-top pair density via auxiliary spin densities. The latter allows for reducing the self-interaction and the static correlation errors without breaking the spin symmetry. We study the properties and the performance of the non-self-consistent variant of the method, termed lrAC0-postCAS. Numerical demonstration on a set of dissociation energy curves and excitation energies shows that lrAC0-postCAS provides accuracy comparable with more computationally expensive ab initio rivals.
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7 March 2020
Research Article|
March 02 2020
Long-range-corrected multiconfiguration density functional with the on-top pair density
Michał Hapka
;
Michał Hapka
1
Institute of Physics, Lodz University of Technology
, ul. Wolczanska 219, 90-924 Lodz, Poland
2
Faculty of Chemistry, University of Warsaw
, ul. L. Pasteura 1, 02-093 Warsaw, Poland
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Ewa Pastorczak
;
Ewa Pastorczak
1
Institute of Physics, Lodz University of Technology
, ul. Wolczanska 219, 90-924 Lodz, Poland
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Agnieszka Krzemińska
;
Agnieszka Krzemińska
1
Institute of Physics, Lodz University of Technology
, ul. Wolczanska 219, 90-924 Lodz, Poland
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Katarzyna Pernal
Katarzyna Pernal
a)
1
Institute of Physics, Lodz University of Technology
, ul. Wolczanska 219, 90-924 Lodz, Poland
a)Author to whom correspondence should be addressed: pernalk@gmail.com
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a)Author to whom correspondence should be addressed: pernalk@gmail.com
J. Chem. Phys. 152, 094102 (2020)
Article history
Received:
November 16 2019
Accepted:
February 11 2020
Citation
Michał Hapka, Ewa Pastorczak, Agnieszka Krzemińska, Katarzyna Pernal; Long-range-corrected multiconfiguration density functional with the on-top pair density. J. Chem. Phys. 7 March 2020; 152 (9): 094102. https://doi.org/10.1063/1.5138980
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