Matrix effects on hydroxy-group vibrational frequencies caused by weak intermolecular interactions

Abstract
Matrix effects on the frequencies of i.r. vibrations of hydroxy and deuteroxy groups in CH3OH and D2O have been studied. Band shifts, Δν, show a linear dependence on √Tc(where Tc is the critical temperature) of the substance comprising the matrix, as a measure of the intermolecular potential. Within a homologous series Δν is more sensitive to hydrogen bonding than to van der Waals interactions. This implies that the application of the Badger–Bauer rule to hydrogen-bonded systems must take non-polar solvents as frequency standard and not the vapour state. The bending mode of D2O shows different changes: it has a red-shifted matrix effect and is blue-shifted by hydrogen bonds.

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