Abstract
Vibrational spectra in the range 200–3000 cm −1 are reported and assigned for the species (CH 3) 2PH, (CH 3) 2PD, (CD 3) 2PH, (CD 3) 2PD, CH 3CD 3PH and CH 3CD 3PD. The spectra in the range 1020–500 cm −1 are complicated due to the coupling between δPH, ϱMe and the skeletal modes of the molecule. Interpretation is only possible through a force field which is markedly different from an earlier one of dimethyl sulphide. This force field predicts uncoupled δPH frequencies of 835 ( a) and 909 cm −1 ( a), couples PH bending largely to out-of-skeletal plane methyl rocking (ϱ i) and includes a low p¦¦( a) bending constant, a high skeletal bending constant and unusual signs for two interaction constants. In the crystalline phase at 78 K, the two methyl groups are non-equivalent.
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