A femtosecond velocity map imaging study on B-band predissociation in CH 3I. II. the 2 0 1 and 3 0 1 vibronic levels

Abstract

Femtosecond time-resolved velocity map imaging experiments are reported on several vibronic levels of the second absorption band (B-band) of CH 3I, including vibrational excitation in the 2 and 3 modes of the bound 3R 1(E) Rydberg state. Specific predissociation lifetimes have been determined for the 201 and 301 vibronic levels from measurements of time-resolved I*( 2P 12) and CH 3 fragment images, parent decay, and photoelectron images obtained through both resonant and non-resonant multiphoton ionization. The results are compared with our previously reported predissociation lifetime measurements for the band origin 000 [Gitzinger, J. Chem. Phys. 132, 234313 (2010)10.1063/1.3455207]. The result, previously reported in the literature, where vibrational excitation to the C-I stretching mode ( 3) of the CH 3I 3R 1(E) Rydberg state yields a predissociation lifetime about four times slower than that corresponding to the vibrationless state, whereas predissociation is twice faster if the vibrational excitation is to the umbrella mode ( 2), is confirmed in the present experiments. In addition to the specific vibrational state lifetimes, which were found to be 0.85 0.04 ps and 4.34 0.13 ps for the 201 and 301 vibronic levels, respectively, the time evolution of the fragment anisotropy and the vibrational activity of the CH 3 fragment are presented. Additional striking results found in the present work are the evidence of ground state I( 2P 32) fragment production when excitation is produced specifically to the 301 vibronic level, which is attributed to predissociation via the A-band 1Q 1 potential energy surface, and the indication of a fast adiabatic photodissociation process through the repulsive A-band 3A 1(4E) state, after direct absorption to this state, competing with absorption to the 301 vibronic level of the 3R 1(E) Rydberg state of the B-band.