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The electronic structure and energetics of V+-benzene half-sandwiches of different multiplicities: Comparative multireference and single-reference theoretical studyстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Polestshuk Pavel M., Dem’yanov Piotr I., Ryabinkin Ilya G.
- Журнал: Journal of Chemical Physics
- Том: 129
- Номер: 5
- Год издания: 2008
- Издательство: AIP Publishing
- Местоположение издательства: United States
- Первая страница: 054307
- DOI: 10.1063/1.2955741
- Аннотация: Multireference complete active space self-consistent field CASSCF and multiconfigurational quasidegenerate perturbation theory MCQDPT and single-reference ab initio Møller–Plesset second order perturbation theory MP2 and coupled clusters with singles, doubles and noniterative triples CCSDT and density functional theory PBE and B3LYP electronic structure calculations of VC6H6+ half-sandwich in the states of different multiplicities are described and compared. Detailed analyses of the geometries and electronic structures of the all found states are given; adiabatic and diabatic dissociation energies are estimated. The lowest electronic state of VC6H6+ half-sandwich was found to be the quintet 5B2 state with a slightly deformed upside-down-boat-shaped benzene ring and d4 configuration of V atom, followed by a triplet 3A2 state lying about 4 kcal/mol above. The lowest singlet state 1A1d4 lies much 28 kcal/mol higher. MCQDPT calculated adiabatic dissociation energy 53.6 kcal/mol for the lowest 5B2d4 state agrees well with the current 56.4 54.4 kcal/mol experimental estimate, giving a preference to the lower one. Compared to MCQDPT, B3LYP hybrid exchange-correlation functional provides the best results, while CCSDT performs usually worse. Gradient-corrected PBE calculations tend to systematically overestimate metal-benzene binding in the row quintettripletsinglet.
- Добавил в систему: Демьянов Петр Игнатьевич