Rotationally resolved (3 + 1) rempi of H_2 via the B^1Σ^+_u state

Abstract

In the paper, we compare the results of our ab initio calculations for the ro-vibrational branching ratios resulting from a (3+1) REMPI of H_2 via the B^1Σ^+_u state with the experimental data of Pratt, Poliakoff, Dehmer and Dehmer. These results indicate that non-Franck-Condon effects are less important here than in the (3+1) REMPI of H_2 via the C^1Π_u state. We observe that the ΔJ = ±3 peaks in the photoelectron spectrum are of negligible strength and that the ratio of ΔJ = +1 to ΔJ = −1 peak is independent of the ionic vibrational state. A detailed analysis indicates that these features arise as a result of a dynamic interference between the do and dμ ionization channels and do not imply either the smallness of the d-wave or the smallness of the j_t = 3 angular momentum coupling terms.

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