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Pair‐Density Functional Theory Based on Spin‐Projected Unrestricted Hartree‐Fock Method: A Density‐Corrected Version.

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Title: Pair‐Density Functional Theory Based on Spin‐Projected Unrestricted Hartree‐Fock Method: A Density‐Corrected Version.
Authors: Wang, Shirong1 (AUTHOR), Xu, Xin1,2 (AUTHOR) xxchem@fudan.edu.cn
Source: Journal of Computational Chemistry. 5/30/2026, Vol. 47 Issue 14, p1-9. 9p.
Subjects: Density functional theory, Hartree-Fock approximation, Electron configuration, Bond energy (Chemistry), Transition metal compounds, Quantum chemistry, Electronic structure
Abstract: Achieving an accurate yet computationally efficient treatment of both static and dynamic electron correlation remains a central challenge in quantum chemistry. This work introduces a density‐corrected (DC) version of the recently proposed pair‐density functional theory based on the spin‐projected unrestricted Hartree‐Fock method (SU‐PDFT). SU‐PDFT combines spin‐projected unrestricted Hartree‐Fock (SUHF) with an on‐top pair‐density functional, offering a cost‐effective alternative to multiconfiguration pair‐density functional theory (MC‐PDFT). While SU‐PDFT provides moderate accuracy, it exhibits significant errors for properties such as spin splittings and transition‐metal bond dissociation energies. Inspired by density‐corrected DFT, we proposed here the density‐corrected SU‐PDFT (DC‐SU‐PDFT) method, which incorporates a density functional theory contribution in the self‐consistent step, yielding a pseudo‐spin density of higher quality. Benchmarks demonstrate that DC‐SU‐PDFT generally improves upon SU‐PDFT for spin splittings, bond dissociation energies of diatomic molecules, and isomerization energies, achieving an overall accuracy comparable to that of MC‐PDFT while retaining a favorable computational cost. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:Achieving an accurate yet computationally efficient treatment of both static and dynamic electron correlation remains a central challenge in quantum chemistry. This work introduces a density‐corrected (DC) version of the recently proposed pair‐density functional theory based on the spin‐projected unrestricted Hartree‐Fock method (SU‐PDFT). SU‐PDFT combines spin‐projected unrestricted Hartree‐Fock (SUHF) with an on‐top pair‐density functional, offering a cost‐effective alternative to multiconfiguration pair‐density functional theory (MC‐PDFT). While SU‐PDFT provides moderate accuracy, it exhibits significant errors for properties such as spin splittings and transition‐metal bond dissociation energies. Inspired by density‐corrected DFT, we proposed here the density‐corrected SU‐PDFT (DC‐SU‐PDFT) method, which incorporates a density functional theory contribution in the self‐consistent step, yielding a pseudo‐spin density of higher quality. Benchmarks demonstrate that DC‐SU‐PDFT generally improves upon SU‐PDFT for spin splittings, bond dissociation energies of diatomic molecules, and isomerization energies, achieving an overall accuracy comparable to that of MC‐PDFT while retaining a favorable computational cost. [ABSTRACT FROM AUTHOR]
ISSN:01928651
DOI:10.1002/jcc.70398