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Nitranilic acid hexahydrate, a novel benchmark system of the Zundel cation in an intrinsically asymmetric environment: hydrogen bond dynamics characterised by experimental and theoretical methodsстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
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Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 23 ноября 2017 г.
- Авторы: Molčanov K., Stare J., Vener M.V., Kojić-Prodić B., Mali G., Grdadolnik J., Mohaček-Grošev V.
- Журнал: Physical Chemistry Chemical Physics
- Том: 16
- Год издания: 2014
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 998
- Последняя страница: 1007
- DOI: 10.1039/c3cp54026j
- Аннотация: Nitranilic acid (2,5-dihydroxy-3,6-dinitro-2,5-cyclohexadiene-1,4-dione) as a strong dibasic acid in acidic aqueous media creates the Zundel cation, H5O2+. The structural unit in a crystal comprises (H5O2)2+(2,5-dihydroxy-3,6-dinitro-1,4-benzoquinonate)2 dihydrate where the Zundel cation reveals no symmetry, being an ideal case for studying proton dynamics and its stability. The Zundel cation and proton transfer dynamics are studied by variable-temperature X-ray diffraction, IR and solid-state NMR spectroscopy, and various quantum chemical methods, including periodic DFT calculations, ab initio molecular dynamics simulation, and quantization of nuclear motion along three fully coupled internal coordinates. The Zundel cation features a short H-bond with the O O distance of 2.433(2) Å with an asymmetric placement of hydrogen. The proton potential is of a single well type and, due to the non-symmetric surroundings, of asymmetric shape. The formation of the Zundel cation is facilitated by the electronegative NO2 groups. The employed spectroscopic techniques supported by calculations confirm the presence of a short H-bond with a complex proton dynamics.
- Добавил в систему: Венер Михаил Владимирович