Abstract
Raman spectra are presented for liquid (CH 3) 3P, single crystal (CH 3) 3PS and sublimed films of (CH 3) 3P, (CH 3) 3PO, (CH 3) 3PS and (CH 3) 3PSe. Vibrational assignments are offered for all compounds and, by means of low temperature spectroscopy and isotopic substitution, both the A 2 and E torsional frequencies are identified. Tests of several common models used to deduce potential barrier parameters are made, and it is found that inclusion of some mixing between the torsional and skeletal bending coordinates can change the barrier values by as much as 10%. Methyl—methyl interaction terms are even more sensitive to the potential model used. Barrier values of 1100, 1460, 1280 and 1160 cm −1 are obtained for (CH 3) 3P, (CH 3) 3PO, (CH 3) 3PS and (CH 3) 3PSe respectively while the corresponding top—top coupling terms are −92, −213, −67 and −57 cm −1. The magnitudes and signs of these potential parameters are discussed in terms of nonbonded interactions between methyl hydrogens and the other atoms in the molecules.
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