Combinatorial Broadening Mechanism of O–H Stretching Bands in H-Bonded Molecular Clusters

• Published in: Journal of applied spectroscopy Vol. 83; no. 3; pp. 350 - 357
• Main Authors: Pitsevich, G. A., Doroshenko, I. Yu, Pogorelov, V. E., Pettersson, L. G. M., Sablinskas, V., Sapeshko, V. V., Balevicius, V.
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.07.2016; Springer
• Subjects: absorption-band half-width; Analysis; Analytical Chemistry; Atomic/Molecular Structure and Spectra; Bonds (Securities); H-bonding; Hydrogen bonds; molecular cluster; Physics; Physics and Astronomy
• ISSN: 0021-9037; 1573-8647; 1573-8647
• DOI: 10.1007/s10812-016-0293-2

A new mechanism for combinatorial broadening of donor-OH stretching-vibration absorption bands in molecular clusters with H-bonds is proposed. It enables the experimentally observed increase of the O–H stretching-vibration bandwidth with increasing number of molecules in H-bonded clusters to be explained. Knowledge of the half-width of the OH stretching-vibration absorption band in the dimer and the number of H-bonds in the analyzed cluster is suffi cient in the zeroth-order approximation to estimate the O–H stretching-absorption bands in clusters containing several molecules. Good agreement between the calculated and published experimental half-widths of the OH stretching-vibration absorption bands in MeOH and PrOH clusters was obtained using this approach.