A complete quantum mechanical study of chlorine photodissociation

A. J. Johnsen, A. B. Alekseyev, G. G. Balint-Kurti, M. Brouard, Alex Brown, R. J. Buenker, E. K. Campbell, D. B. Kokh
2012 Journal of Chemical Physics  
A fully quantum mechanical dynamical calculation on the photodissociation of molecular chlorine is presented. The magnitudes and phases of all the relevant photofragment T-matrices have been calculated, making this study the computational equivalent of a "complete experiment," where all the possible parameters defining an experiment have been determined. The results are used to simulate cross-sections and angular momentum polarization information which may be compared with experimental data.
more » ... calculations rigorously confirm the currently accepted mechanism for the UV photodissociation of Cl 2 , in which the majority of the products exit on the C 1 1u state, with non-adiabatic couplings to the A 3 1u and several other = 1 states, and a small contribution from the B 3 0 + u state present at longer wavelengths. A. Notation The Cl 2 photodissociation processes studied in this paper all correlate to the Cl( 2 P o ) + Cl( 2 P o ) product channel. Due to spin-orbit coupling, the Cl( 2 P o ) atoms can exist in two different J states, Cl( 2 P 3/2 ), and the higher energy Cl( 2 P 1/2 ), separated by 881 cm −1 . Following the notation of Asano and Yabushita, 14 these states will be labelled as Cl( 2 P 3/2 ) ≡ Cl and
doi:10.1063/1.4704829 pmid:22559485 fatcat:nqmhc4ge7rd4hkpc2vu5yslcfm