Kozlovskaya E N, Pitsevich G A, Malevich A E, Doroshenko O P, Pogorelov V E, Doroshenko I Yu, Balevicius V, Sablinskas V, Kamnev A A
Department of Physical Optics, Belarusian State University, Nezavisimosti ave., 4, 220030 Minsk, Belarus.
Department of Physical Optics, Belarusian State University, Nezavisimosti ave., 4, 220030 Minsk, Belarus.
Spectrochim Acta A Mol Biomol Spectrosc. 2018 May 5;196:406-412. doi: 10.1016/j.saa.2018.01.071. Epub 2018 Jan 31.
Raman spectra of liquid water and ice were measured at different temperatures. The intensity of the band assigned to bending vibrations of water molecules was observed to decrease at the liquid-to-solid transition, while the Raman line near 2200cm showed an anomalously high intensity in the solid phase. A tetrahedral model was used for computer analysis of the observed spectral changes. Quantum-chemical calculations of the structure, normal vibrations and Raman spectra in the harmonic approximation, as well as frequencies and intensities of some vibrations using 1D and 2D potential energy surfaces, were carried out using B3LYP with the cc-pVTZ basis set. The influence of the number of hydrogen bonds on the frequency and Raman activity of the bending vibrations was analyzed. The possibility of hydrogen bond weakening upon excitation of the combined bending-rocking vibration due to the large amplitude of this vibration is considered.
在不同温度下测量了液态水和冰的拉曼光谱。观察到，在液-固转变时，归属于水分子弯曲振动的谱带强度降低，而在2200cm附近的拉曼线在固相表现出异常高的强度。使用四面体模型对观察到的光谱变化进行计算机分析。采用B3LYP/cc-pVTZ基组，对结构、简正振动和拉曼光谱进行了量子化学计算，并使用一维和二维势能面计算了一些振动的频率和强度。分析了氢键数量对弯曲振动频率和拉曼活性的影响。考虑了由于组合弯曲-摇摆振动的大振幅，在该振动激发时氢键减弱的可能性。
