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Koopmans’ Theorem in the Hartree-Fock Method. General Formulation Научная публикация

Журнал Journal of Chemical Physics
ISSN: 0021-9606 , E-ISSN: 1089-7690
Вых. Данные Год: 2018, Том: 148, Номер: 9, Номер статьи : 094101, Страниц : 17 DOI: 10.1063/1.5019330
Ключевые слова self-consistent-field; direct configuration-interaction; determinant wave-functions; coupling operator method; multiple active spaces; open-shells; perturbation-theory; basis-sets; icosahedral symmetry; variable occupations
Авторы Plakhutin Boris N. 1
Организации
1 Laboratory of Quantum Chemistry, Boreskov Institute of Catalysis, Russian Academy of Sciences, Novosibirsk 630090, Russian Federation

Информация о финансировании (2)

1 Федеральное агентство научных организаций России 0303-2016-0001
2 Российский фонд фундаментальных исследований 15-03-00830

Реферат: This work presents a general formulation of Koopmans’ theorem (KT) in the Hartree-Fock (HF) method which is applicable to molecular and atomic systems with arbitrary orbital occupancies and total electronic spin including orbitally degenerate (OD) systems. The newformulation is based on the full set of variational conditions imposed upon the HF orbitals by the variational principle for the total energy and the conditions imposed by KT on the orbitals of an ionized electronic shell [B. N. Plakhutin and E. R. Davidson, J. Chem. Phys. 140, 014102 (2014)]. Based on these conditions, a general form of the restricted open-shell HF method is developed, whose eigenvalues (orbital energies) obey KT for the whole energy spectrum. Particular attention is paid to the treatment of OD systems, for which the new method gives a number of unexpected results. For example, the present method gives four different orbital energies for the triply degenerate atomic level 2p in the second row atoms B to F. Based on both KT conditions and a parallel treatment of atoms B to F within a limited configuration interaction approach, we prove that these four orbital energies, each of which is triply degenerate, are related via KTto the energies of different spin-dependent ionization and electron attachment processes (2p)N !(2p)N1. A discussion is also presented of specific limitations of the validity of KT in the HF method which arise in OD systems. The practical applicability of the theory is verified by comparing KT estimates of the ionization potentials I2s and I2p for the second row open-shell atoms Li to F with the relevant experimental data. Published by AIP Publishing
Библиографическая ссылка: Plakhutin B.N.
Koopmans’ Theorem in the Hartree-Fock Method. General Formulation
Journal of Chemical Physics. 2018. V.148. N9. 094101 :1-17. DOI: 10.1063/1.5019330 WOS Scopus РИНЦ CAPlusCA OpenAlex
Даты:
Поступила в редакцию: 13 дек. 2017 г.
Принята к публикации: 9 февр. 2018 г.
Опубликована online: 1 мар. 2018 г.
Опубликована в печати: 7 мар. 2018 г.
Идентификаторы БД:
Web of science: WOS:000427030500004
Scopus: 2-s2.0-85042757323
РИНЦ: 35495556
Chemical Abstracts: 2018:364703
Chemical Abstracts (print): 169:80221
OpenAlex: W2790559611
Цитирование в БД:
БД Цитирований
Web of science 10
Scopus 15
РИНЦ 12
OpenAlex 17
Альметрики: