Assignments of Rydberg and valence transitions in the electronic absorption spectrum of dimethyl sulfide

Abstract

The electronic absorption spectra of (CH3)2S and (CD3)2S have been recorded between 1250 and 2500 Å. Twenty-four of the observed transitions have been arranged into three Rydberg series originating from the b1 nonbonding orbital. These Rydberg series have been identified as one s, one p and one d series. From their isotope zero point energy shifts and observed vibronic structures, the Rydberg states were deduced to be contaminated by other states. Two unmistakenly non-Rydberg transitions were observed. From solution and solvent shift data, they were proposed to arise from promotions out of the a1 bonding orbital.