Time- and frequency-resolved photoionisation of the allyl radical

We report picosecond time-resolved pump-probe photoelectron spectra of the allyl radical, C3H5, and the fully deuterated allyl, C3D5, carried out in order to elucidate the primary photophysical processes upon UV excitation. It is shown that the UV bands of allyl decay in a two-step process: the first step is an internal conversion to the lower-lying A-state within 20 ps or less, while the second step is a very fast decay from the A-state to the electronic ground state through a conical intersection. In addition we report the first zero kinetic energy (ZEKE) photoelectron spectrum of allyl, yielding an ionisation energy of 65762 cm(-1).