Shapes of the ν1 Band of Liquid Chloroform and Intermolecular Interaction

Abstract The infrared absorption spectrum for the ν1 fundamental of chloroform or chloroform-d shows strong asymmetry, with a remarkable tailing on the high-frequency side. The observed band-width of the ν1 fundamental of chloroform-d is significantly narrower than that of chloroform. These asymmetric band profiles of the ν1 bands of chloroform and chloroform-d can be interpreted in terms of the existence of two different types of chloroform molecules. One is a molecule which interacts with another molecule, and the other is a non-interacting molecule. The isotope effect on the band-width can be explained in terms of the difference in the reduced mass for chloroform and chloroform-d.

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