dorsal/arxiv
View SchemaWhen Density Functional Theory goes wrong and how to fix it: spin balanced unrestricted Kohn-Sham formalism
| Authors | Artem Masunov |
|---|---|
| Categories | |
| ArXiv ID | physics/0310106 |
| URL | https://arxiv.org/abs/physics/0310106 |
Abstract
Kohn-Sham (KS) formalism of Density Functional Theory is modified to include the systems with strong non-dynamic electron correlation. Unlike in extended KS and broken symmetry unrestricted KS formalisms, cases of both singlet-triplet and aufbau instabilities are covered, while preserving a pure spin-state. The straightforward implementation is suggested, which consists of placing spin constraints on complex unrestricted Hartree-Fock wave function. Alternative approximate approach consists of using the perfect pairing implementation with the natural orbitals of unrestricted KS method and square roots of their occupation numbers as configuration weights without optimization, followed by a posteriori exchange-correlation correction. The numerical results of this approximation for the barrier to the internal rotation in ethylene are reported to be in close agreement with experimental data.
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"date_created": "2026-03-02T18:00:46.601000Z",
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"abstract": "Kohn-Sham (KS) formalism of Density Functional Theory is modified to include\nthe systems with strong non-dynamic electron correlation. Unlike in extended KS\nand broken symmetry unrestricted KS formalisms, cases of both singlet-triplet\nand aufbau instabilities are covered, while preserving a pure spin-state. The\nstraightforward implementation is suggested, which consists of placing spin\nconstraints on complex unrestricted Hartree-Fock wave function. Alternative\napproximate approach consists of using the perfect pairing implementation with\nthe natural orbitals of unrestricted KS method and square roots of their\noccupation numbers as configuration weights without optimization, followed by a\nposteriori exchange-correlation correction. The numerical results of this\napproximation for the barrier to the internal rotation in ethylene are reported\nto be in close agreement with experimental data.",
"arxiv_id": "physics/0310106",
"authors": [
"Artem Masunov"
],
"categories": [
"physics.chem-ph"
],
"title": "When Density Functional Theory goes wrong and how to fix it: spin balanced unrestricted Kohn-Sham formalism",
"url": "https://arxiv.org/abs/physics/0310106"
},
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