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Comment on possible motional effects on the vibrational spectrum of water in the fundamental stretching region

Authors
Journal
Spectrochimica Acta Part A Molecular Spectroscopy
0584-8539
Publisher
Elsevier
Publication Date
Volume
28
Issue
5
Identifiers
DOI: 10.1016/0584-8539(72)80069-2

Abstract

Abstract The i.r. spectrum of water in four organic solvents has been carefully recorded in the v(OH) region. Dipole correlation functions obtained through Fourier transform of the high-frequency side of the v 3 band confirm essentially free rotation of water in the two non-polar solvents chloroform and carbontetrachloride, on a time scale of the order 0.1 psec. In dioxane solution, a shoulder observed on the high-frequency side of the v 3 band, similar to that observed in the pure liquid, is assigned to non-H-bonded molecules. It is suggested that exchange motions between free and H-bonded species in dioxane solution and in the pure liquid, affect the position and width of this shoulder component, and also the overall band shapes. The effect occurs on a time-scale of the order 0.1 psec.

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