We have obtained transient resonance Raman spectra of the [CH2CHCH2](+) (allyl cation) produced following C-band excitation of cyclopropyl bromide. The experimental resonance Raman spectrum display an overtone progression in the nominal [C=C=C](+) stretch mode and its combination bands with the CH/CH2 rocking modes. Density functional theory computations were performed to estimate the vibrational frequencies for the allyl cation, the allyl radical, the cyclopropyl radical, the cyclopropyl bromide molecule and the gauche-allyl bromide molecule and compared to the experimental vibrational frequencies. This comparison indicates that the allyl cation can be formed as a product of cyclopropyl bromide photodissociation in acetonitrile solution. (C) 2002 Elsevier Science B.V. All rights reserved.