Product fine structure state populations and nonadiabatic dissociation dynamics: Cl*(2P1/2)/Cl(2P3/2) branching ratio in the visible and near ultraviolet photodissociation of nitrosyl chloride

Abstract

Chlorine atoms in their 2Pj states were observed using resonance-enhanced multiphoton ionization and time-of-flight techniques, following the photodissociation of nitrosyl chloride at preselected wavelengths (i.e., 600, 562, 478, and 355 nm). The fine structure branching ratio and the spatial anisotropy parameter were determined. Combining these observations with results from previous studies, a complete picture about product fine structure state populations is obtained. The observed fine structure populations are explained with the aid of a new correlation diagram in the Cs point group. The adiabatic, nonadiabatic, and diabatic dissociation dynamics involving several avoided crossings at large interfragment separations are discussed.