Solid-State Vibrational Spectra of the Methyl and Methyl-d3 Halides

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Abstract
The vibrational fundamentals of solid CH3Cl, CH3Br, and CH3I and of their fully deuterated counterparts have been examined at 77°K under high resolution. CH3Cl35 has been synthesized and its ν3 spectrum compared to that of ordinary CH3Cl, permitting the assignment of the CH3Cl35 and CH3Cl37 contributions in the ν3 multiplet structure. The relative intensities of absorption in 1:1 CH3X:CD3X solid solutions have been measured to test the relationship between splitting, frequency, and absorption intensity predicted by the dipolar correlation model. The test proved to be insensitive. A study of the ν3 absorption of each component in CH3Cl:CD3Cl solid solutions throughout the concentration range has shown that multiplet splitting persists at concentrations as low as 1%.