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Environmental effects on vibrational proton dynamics in H5O2+: DFT study on crystalline H5O2+ClO4−статья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 8 сентября 2021 г.
- Авторы: Vener Mikhail V., Sauer Joachim
- Журнал: Physical Chemistry Chemical Physics
- Том: 7
- Номер: 2
- Год издания: 2005
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 258
- Последняя страница: 263
- DOI: 10.1039/B412795A
- Аннотация: The structure as well as IR and inelastic neutron scattering (INS) spectra of H5O2+ in crystalline H5O2+ClO4− were simulated using Car–Parrinello molecular dynamics with the BLYP functional. The potential of the O⋯H+⋯O fragment is very shallow. The Pnma structure, assumed in the X-ray study to be the most suitable choice, is a saddle point on the potential energy surface, while the P212121 minimum structure is only 20 cm−1 lower in energy. The computed INS and IR spectra enable us to achieve a complete assignment of the observed spectra. The broad band between 1000 and 1400 cm−1 is due to the asymmetric stretch and one of the bending vibrations of the O⋯H+⋯O fragment, while the band between 1600 and 1800 cm−1 is due to the bending vibration of the water molecules and the second bending of the O⋯H+⋯O fragment. Comparison with the vibrational spectra of isolated H5O2+, obtained using Born–Oppenheimer molecular dynamics simulation, reveals environmental effects on vibrational proton dynamics in strong H-bonded species. The most pronounced changes are found for the O⋯H+⋯O bending modes because the two bending coordinates become distinctly different for the structure that the H5O2+ ion assumes in the crystal.
- Добавил в систему: Венер Михаил Владимирович