We report the first multiphoton study of the electronic spectrum of the dimethyl sulfide molecule. The interpretation we present is based on analysis of the two-and three-photon resonance enhanced multiphoton ionisation (REMPI) spectra and measurements of the kinetic energies of the photoelectrons resulting from the REMPI process. Members of four (possibly five) Rydberg series are identified and a refined value of the first ionisation limit of dimethyl sulfide is obtained: E i = 8.710 & 0.005 eV (70250 & 40 cm-'). As in our previous study of the related divalent sulfide methanethiol, we detect the presence of slower electrons in the photoelectron spectra which can be interpreted in terms of near resonant inter-Rydberg state vibronic mixing.

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A recently developed modulation method is used to obtain cross sections for the photoionisation of ground state neutral to ground state ionic, atomic and molecular chlorine relative to that of the HCl + (X2n 1IZ,3IZ) +--HCl(X I ~ +) transition at the He Ia wavelength. With the known absolute cross section of the latter process, determined by (e,2e) coincidence spectroscopy, the present ell,periments provide absolute photoionisation cross sections of the CI + epz,l,o) +--Clep) and Cli (X Z n g, 1IZ,3 IZ) +--Cl z (X I ~ t) transitions. Relative cross sections, previously determined for the transitions to the additional Cl and Cl z ionic states accessible with He Ia radiation, are used to obtain absolute cross sections for the Cl+(IDz, ISO) +--Clep) and Cli(AZnu,1IZ,3IZ, BZ~t) +--Clz(XI~t) ionisation processes.

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