|
ИСТИНА |
Войти в систему Регистрация |
ИПМех РАН |
||
Ab initio study of molecular structure and internal rotation in methyldicyanophosphine and methyldiisocyanophosphine. The Raman spectrum of methyldicyanophosphine and its interpretation with the use of scaling of ab initio force fieldsстатья
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: Khaikin L.S., Grikina O.E., Zhilinskii B.I., Zhilinskaya E.A., Baskir E.G., Nepomnyashchii R.V., Fomicheva O.A., Proskurnina M.V.
- Журнал: Russian Chemical Bulletin
- Том: 47
- Номер: 9
- Год издания: 1998
- Издательство: Springer Nature
- Местоположение издательства: Switzerland
- Первая страница: 1653
- Последняя страница: 1665
- DOI: 10.1007/BF02495681
- Аннотация: The equilibrium geometric parameters and structures of transition states of internal rotation for the molecules of methyldicyanophospine MeP(CN)(2) and its isocyano analog MeP(NC)2 were calculated by the RHF and MP2 methods with the 6-31G* and 6-31G** basis sets. At the MP2 level, the total energy of cyanide is similar to 35 kcal mol(-1) lower than that of isocyanide and the barriers to internal rotation of methyl group for MeP(CN)2 and MeP(NC)2 are 2.2 and 2.7 kcal mol(-1) respectively. For both molecules, the one-dimensional ab initio potential functions of internal rotation approximated by a truncated Fourier series were used to determine the frequencies of torsional transitions by solving direct vibrational problems for a non-rigid model. The Raman spectrum of crystalline MeP(CN)2 was recorded in the range 3500-50 cm(-1). The vibrational spectra of this compound were interpreted by scaling ab initio force fields calculated by the RHF and MP2 methods. The vibrational spectrum of methyldiisocyanophosphine was predicted with the use of the obtained scale factors.
- Добавил в систему: Хайкин Леонид Соломонович