Exact decompositions of the total KS-DFT exchange–correlation energy into one- and two-center terms
dc.contributor.author
dc.date.accessioned
2024-03-20T08:23:13Z
dc.date.available
2024-03-20T08:23:13Z
dc.date.issued
2023-06-16
dc.identifier.issn
0021-9606
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dc.description.abstract
In the so-called Interacting Quantum Atoms (IQA) approach, the molecular energy is numerically decomposed as a sum of atomic and diatomic contributions. While proper formulations have been put forward for both Hartree–Fock and post-Hartree–Fock wavefunctions, this is not the case for the Kohn–Sham density functional theory (KS-DFT). In this work, we critically analyze the performance of two fully additive approaches for the IQA decomposition of the KS-DFT energy, namely, the one from Francisco et al., which uses atomic scaling factors, and that from Salvador and Mayer based upon the bond order density (SM-IQA). Atomic and diatomic exchange–correlation (xc) energy components are obtained for a molecular test set comprising different bond types and multiplicities and along the reaction coordinate of a Diels–Alder reaction. Both methodologies behave similarly for all systems considered. In general, the SM-IQA diatomic xc components are less negative than the Hartree–Fock ones, which is in good agreement with the known effect of electron correlation upon (most) covalent bonds. In addition, a new general scheme to minimize the numerical error of the sum of two-electron energy contributions (i.e., Coulomb and exact exchange) in the framework of overlapping atoms is described in detail
dc.description.sponsorship
Financial support has been furnished by the Ministerio de Ciencia, Innovación y Universidades (MCIU), Grant No. PGC2018-098212-B-C22. M.G. acknowledges the Generalitat de Catalunya and Fons Social Europeu for the predoctoral fellowship (Grant No. 2018 FI_B 01120)
Open Access funding provided thanks to the CSUC agreement with American Institut of Physics (AIP)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Institute of Physics (AIP)
dc.relation
PGC2018-098212-B-C22
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Reproducció digital del document publicat a: https://doi.org/10.1063/5.0142778
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The Journal of Chemical Physics, 2023, vol. 158, núm. 23, p. 234105
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Articles publicats (D-Q)
dc.rights
Attribution 4.0 International
dc.rights.uri
dc.title
Exact decompositions of the total KS-DFT exchange–correlation energy into one- and two-center terms
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.relation.projectID
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-098212-B-C22/ES/DESCOMPOSICION EN EL ESPACIO REAL DE PROPIEDADES OPTICAS NO LINEALES PARA EL DISEÑO RACIONAL DE MATERIALES OPTOELECTRONICOS/
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
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dc.relation.ProjectAcronym
dc.identifier.eissn
1089-7690