Abstract
The vacuum ultraviolet absorption (from 220 to 120 nm) and photoelectron (from 6 to 21 eV) spectra of the following molecules are compared: tetrahydropyran, tetrahydrothiopyran, methylvinylether, methylvinylthioether, dihydropyran, and 4,4-dimethyl-2,3-dihydrothiopyran. The great similarity between the photoelectron spectra of related ethers and thioethers is stressed. In the case of saturated thioethers the corresponding ultraviolet spectra are, however, very different, showing that the involvement of 3d orbitals is important in the low excited states of saturated sulfur compounds. The uv spectrum of tetrahydrothiopyran is interpreted in terms of at least five closely spaced Rydberg series that are of the s, p, or d type. They all converge to the first (S 3p) ionization potential. Both unsaturated ethers and thioethers have one π* ← π band on which s-, p-, and d-type Rydberg series converging to the first (π-type) IP are superimposed. There is no evidence for the participation of S 3d AO's in the low lying excited states of unsaturated thioethers.
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