Raman spectroscopic and theoretical study of liquid and solid water within the spectral region 1600-2300cm-1

E N Kozlovskaya; G A Pitsevich; A E Malevich; O P Doroshenko; V E Pogorelov; I Yu Doroshenko; V Balevicius; V Sablinskas; A A Kamnev

doi:10.1016/j.saa.2018.01.071

Raman spectroscopic and theoretical study of liquid and solid water within the spectral region 1600-2300cm^-1

Spectrochim Acta A Mol Biomol Spectrosc. 2018 May 5:196:406-412. doi: 10.1016/j.saa.2018.01.071. Epub 2018 Jan 31.

Authors

E N Kozlovskaya¹, G A Pitsevich², A E Malevich¹, O P Doroshenko³, V E Pogorelov³, I Yu Doroshenko³, V Balevicius⁴, V Sablinskas⁴, A A Kamnev⁵

Affiliations

¹ Department of Physical Optics, Belarusian State University, Nezavisimosti ave., 4, 220030 Minsk, Belarus.
² Department of Physical Optics, Belarusian State University, Nezavisimosti ave., 4, 220030 Minsk, Belarus. Electronic address: pitsevich@mail.ru.
³ Faculty of Physics, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine.
⁴ Faculty of Physics, Vilnius University, Sauletekio al. 9-3, LT-10222 Vilnius, Lithuania.
⁵ Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, Prosp. Entuziastov, 13, 410049 Saratov, Russia. Electronic address: aakamnev@ibppm.ru.

PMID: 29499569
DOI: 10.1016/j.saa.2018.01.071

Abstract

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^-1 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.

Keywords: Discrete variable representation (DVR); Intensities of Raman lines; PES; Raman spectra; Water.