The C-, D-, and E-band resonance Raman spectra were obtained for nickel methyl xanthate (NMX) in acetonitrile solution. Density functional calculations were carried out to help elucidate its ultraviolet electronic transitions and vibrational assignments of the resonance Raman spectra associated with the C-, D-, and E-band absorptions. The Franck–Condon region photodissociation dynamics of NMX in C, D, and E-band absorptions were revealed to have multidimensional characters and to be significantly different from one another in terms of the resonance Raman intensity patterns. The photofragmentation mechanism associated with C-, D-, and E-band absorptions are briefly discussed. Copyright © 2010 John Wiley & Sons, Ltd.