Predissociation dynamics of the O2 B 3Σ−u state: Vibrational state dependence of the product fine‐structure distribution

Autor: D. R. Cyr, Daniel M. Neumark, David J. Leahy, David L. Osborn
Rok vydání: 1995
Předmět:
Zdroj: The Journal of Chemical Physics. 103:2495-2508
ISSN: 1089-7690
0021-9606
DOI: 10.1063/1.469671
Popis: The predissociation of the O2B 3Σ−u state (υ=0–11) is investigated using fast beam photofragment translational spectroscopy. The energy resolution of the experiment, 7–10 meV, is sufficient to yield the correlated fine structure distribution P(j1,j2) for the two O(3Pj) fragments. These spin–orbit branching ratios depend markedly on the vibrational quantum number, providing detailed insight into a relatively unexplored facet of molecular dissociation dynamics. No less than four repulsive states are expected to mediate the predissociation of the B 3Σ−u state, primarily via spin–orbit coupling, and the couplings among these states at long range (R∼5–7 A) determine the final spin–orbit distributions P(j1,j2). We have attempted to model these distributions in both the adiabatic and diabatic limits, with neither limit proving very successful. A more phenomenological approach to fitting our data suggests that products with j1=j2=2 result from single transitions between adiabatic potentials at long range, whereas...
Databáze: OpenAIRE