Spectral signs of the internal heavy-atom effect in aliphatic carbonyl compounds

The CNDO/S method has been applied to the internal effect of Si on the electronic spectrum of the acetone molecule; there is a considerable bathochromic shift and an increase in the \(S_0 \to S_{n\pi ^ * } \) intensity for theα-silyl ketones, while theβ-silyl ketons give only an increase in the intensity of \(S_0 \to S_{n\pi ^ * } \) absorption relative to acetone. The heavy atom substantially alters \(f_{S_0 \to T_{n\sigma ^* } } \) and \(\tau _{T_{n\sigma ^* } }^0 \) but has little effect on \(f_{S_0 \to T_{n\pi ^* } } \) and \(\tau _{T_{n\pi ^* } }^0 \) .