Koopmans's Theorem in the Restricted Open-Shell Hartree-Fock Method. II. The Second Canonical Set for Orbitals and Orbital Energies | Sciact - CRIS-система Института катализа

Koopmans's Theorem in the Restricted Open-Shell Hartree-Fock Method. II. The Second Canonical Set for Orbitals and Orbital Energies Научная публикация

Журнал

Journal of Chemical Physics
ISSN: 0021-9606 , E-ISSN: 1089-7690

Вых. Данные

Год: 2010, Том: 132, Номер: 18, Страницы: 184110-184114 Страниц : 5 DOI: 10.1063/1.3418615

Ключевые слова

DENSITY-FUNCTIONAL THEORY; MOLECULAR WAVE-FUNCTIONS; ELECTRONIC-STRUCTURE; SYSTEMS; ANALOG

Авторы

Davidson Ernest R. ¹ , Plakhutin Boris N. ²

Организации

1	Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, USA
2	Laboratory of Quantum Chemistry, Boreskov Institute of Catalysis, Russian Academy of Sciences, Prospekt Lavrentieva 5, Novosibirsk 630090, Russia

Информация о финансировании (2)

1	Российский фонд фундаментальных исследований	09-03-00113
2	Президиум РАН	2009/5.1.9

A treatment of the validity of Koopmans’s theorem (KT) in the restricted open-shell Hartree–Fock (ROHF) method can be separated into two essentially different cases. The first of them involves the one-electron processes X→Xj± in which the spin state of an ion Xj± having a hole or an extra electron in the closed, open or virtual orbital ϕj is correctly described by a one-determinant wave function. This case was analyzed using different methods by Plakhutin et al. [J. Chem. Phys. 125, 204110 (2006)] and by Plakhutin and Davidson [J. Phys. Chem. A 113, 12386 (2009)] . In the present work we analyze more complex processes where the state of an ion cannot be described by a single determinant. An example of such processes is the removal of an alpha electron from the closed shell of a high-spin half-filled open-shell system X. For this case we give a slightly generalized formulation of KT in both the “frozen” orbital approximation (i.e., within the canonical ROHF method) and the limited configuration interaction approach for ionized systems. We also show that a simultaneous treatment of KT for all one-electron ionization processes possible leads to the necessity of introducing in the canonical ROHF method two different sets of orbitals and two respective sets of orbital energies. The theory developed is compared with the previous formulations of KT in the restricted (ROHF) and unrestricted Hartree-Fock methods, and in the unrestricted density functional theory. The practical applicability of the theory is verified by comparing the KT estimates of the vertical ionization potentials in molecules O2 and NO2 with the respective experimental data.

Davidson E.R. , Plakhutin B.N.
Koopmans's Theorem in the Restricted Open-Shell Hartree-Fock Method. II. The Second Canonical Set for Orbitals and Orbital Energies

Journal of Chemical Physics. 2010. V.132. N18. P.184110-184114. DOI: 10.1063/1.3418615 WOS Scopus РИНЦ CAPlusCA OpenAlex

Полный текст от издателя

Поступила в редакцию:	3 янв. 2010 г.
Принята к публикации:	8 апр. 2010 г.
Опубликована в печати:	14 мая 2010 г.
Опубликована online:	14 мая 2010 г.

Web of science:	WOS:000277756500011
Scopus:	2-s2.0-77952715196
РИНЦ:	15313826
Chemical Abstracts:	2010:609181
Chemical Abstracts (print):	152:510888
OpenAlex:	W2007214607

БД	Цитирований
Web of science	22
Scopus	26
РИНЦ	26
OpenAlex	24