Photoabsorption and photodissociation studies of dimethyl sulphoxide (DMSO) in the 35,000-80,000 cm−1 region using synchrotron radiation

•Consolidated study of VUV absorption spectra of DMSO in 35,000-80,000 cm−1 region.•Rydberg series of ns, np and nd type converging to the first three IPs assigned.•Vertical excited states using TDDFT and correlation with experimental energies.•Identification of bands of SO radical produced in photodissociation of DMSO.•First report of VUV absorption spectrum of DMSO-d6.

Photoabsorption and photodissociation studies of dimethyl sulphoxide and its deuterated isotopologue (DMSO-h6 and DMSO-d6) are performed using synchrotron radiation in the 35,000-80,000 cm−1 region. In the photoabsorption spectrum, Rydberg series converging to the first three ionization potentials of DMSO at 9.1, 10.1 and 12.3 eV corresponding to removal of an electron from the highest three occupied molecular orbitals (14a′, 7a″ and 13a′) are observed. Based on a quantum defect analysis, Rydberg series assignments are extended to higher members as compared to earlier works and a few ambiguities in earlier assignments are clarified. Analysis is aided by quantum chemical calculations using the DFT and TDDFT methodologies. Vibronic structures observed in the spectrum of DMSO-h6 in the regions 7.7-8.1 eV and 8.1-8.8 eV are attributed to the transitions 7a″→4p at 7.862 eV and 14a′→6s/4d at 8.182 eV, respectively. Photoabsorption spectra of DMSO-h6 and -d6 recorded using a broad band incident radiation show prominent peaks, which are identified and assigned to electronic and vibronic transitions of the SO radical. This provides a direct confirmation of the fact that DMSO preferentially dissociates into CH3 and SO upon UV-VUV excitation, as proposed in earlier photodissociation studies. An extended vibronic band system associated with the e1Π-X3Σ− transition of the SO radical is identified and assigned. The complete VUV photoabsorption spectrum of DMSO-d6 is also reported here for the first time.