Matrix effects on hydroxy-group vibrational frequencies caused by weak intermolecular interactions
- 1 January 1984
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
- Vol. 80 (5) , 579-588
- https://doi.org/10.1039/f29848000579
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.Keywords
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