Инд. авторы:	Zhukova E.S., Torgashev V.I., Gorshunov B.P., Lebedev V.V., Shakurov G.S., Kremer R.K., Pestrjakov E.V., Thomas V.G., Fursenko D.A., Prokhorov A.S., Dressel M.
Заглавие:	Vibrational states of a water molecule in a nano-cavity of beryl crystal lattice
Библ. ссылка:	Zhukova E.S., Torgashev V.I., Gorshunov B.P., Lebedev V.V., Shakurov G.S., Kremer R.K., Pestrjakov E.V., Thomas V.G., Fursenko D.A., Prokhorov A.S., Dressel M. Vibrational states of a water molecule in a nano-cavity of beryl crystal lattice // Journal of Chemical Physics. - 2014. - Vol.140. - Iss. 22. - Art.224317. - ISSN 0021-9606. - EISSN 1089-7690.
Внешние системы:	DOI: 10.1063/1.4882062; РИНЦ: 23831084;
Реферат:	eng: Low-energy excitations of a single water molecule are studied when confined within a nano-size cavity formed by the ionic crystal lattice. Optical spectra are measured of manganese doped beryl single crystal Mn:Be3Al2Si6O18, that contains water molecules individually isolated in 0.51 nm diameter voids within the crystal lattice. Two types of orientation are distinguished: water-I molecules have their dipole moments aligned perpendicular to the c axis and dipole moments of water-II molecules are parallel to the c-axis. The optical conductivity σ(ν) and permittivity ɛ′(ν) spectra are recorded in terahertz and infrared ranges, at frequencies from several wavenumbers up to ν = 7000 cm−1, at temperatures 5–300 K and for two polarizations, when the electric vector E of the radiation is parallel and perpendicular to the c-axis. Comparative experiments on as-grown and on dehydrated samples allow to identify the spectra of σ(ν) and ɛ′(ν) caused exclusively by water molecules. In the infrared range, well-known internal modes ν 1, ν 2, and ν 3 of the H2O molecule are observed for both polarizations, indicating the presence of water-I and water-II molecules in the crystal. Spectra recorded below 1000 cm−1 reveal a rich set of highly anisotropic features in the low-energy response of H2O molecule in a crystalline nano-cavity. While for E∥c only two absorption peaks are detected, at ∼90 cm−1 and ∼160 cm−1, several absorption bands are discovered for E⊥c, each consisting of narrower resonances. The bands are assigned to librational (400–500 cm−1) and translational (150–200 cm−1) vibrations of water-I molecule that is weakly coupled to the nano-cavity “walls.” A model is presented that explains the “fine structure” of the bands by a splitting of the energy levels due to quantum tunneling between the minima in a six-well potential relief felt by a molecule within the cavity.
Ключевые слова:	beryl crystal lattice; nano-cavity; Vibrational states; Vibrational states of a water molecule;
Издано:	2014
Физ. характеристика:	224317
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