Abstract
Raman spectra are presented for liquid (CH 3) 3As and sublimed films of (CH 3) 3As, (CH 3) 3AsO and (CH 3) 3AsS. Far i.r. spectra are also shown for (CH 3) 3As and (CD 3) 3As and vibrational assignments are offered for all compounds. From spectra of the low temperature films, and by means of isotopic substitution, the A 2 and E torsional frequencies have been identified for most compounds. Potential barrier parameters are calculated for several common models and it is found that an analysis which includes mixing between the E torsion and skeletal bending coordinates is desirable if accurate barriers (better than ∼10%) are sought. Methyl top—top interaction terms are even more sensitive to the potential model used. Barrier values of 820, 1130 and 920 cm −1 are obtained for (CH 3) 3As, (CH 3) 3AsO and (CH 3) 3AsS respectively while the corresponding top—top coupling terms are −91 and −206 cm −1 for (CH 3) 3As and (CH 3) 3AsO. These values are summarized with results for other C 3ν, multi-top molecules and all are discussed in terms of non-bonded interactions between methyl hydrogens and the other atoms in the molecules.
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