The A-band resonance Raman spectra were obtained for methyl xanthate anion in methanol solution. Density functional calculations were done to help elucidate its ultraviolet electronic transitions and to assign the resonance Raman spectra. The results indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion predominantly along the symmetric CS2 stretch, accompanied by the COC stretch, the CH3 wag, the COC scissor, the CS2 scissor, and overtone of the OCS2 out of plane deformation. RCIS/6-31G* calculations were done to predict the distorted geometry structure and the saddle point of methyl xanthate anion in S-3 excited state. (C) 2007 Elsevier B.V. All rights reserved.