Dynamics of dissociative recombination versus electron ejection in single rovibronic resonances of BH

J Chem Phys. 2007 Feb 28;126(8):084301. doi: 10.1063/1.2484107.

Abstract

Optical-optical-optical triple resonance spectroscopy isolates transitions to vibrationless Rydberg states of BH with principal quantum numbers from n=7 to 50. Corresponding resonances appear in the excitation spectrum of excited boron atoms produced by the dissociative relaxation of these states. The decay to neutral products occurs on a nanosecond time scale. Yet, corresponding resonances show Fano coupling widths that approach 1 cm-1. Above threshold, spontaneous ionization dominates, but line shapes match for resonances with the same electron orbital quantum numbers built on v+=0 and v+=1 cores. This striking feature-for-feature similarity in predissociation and autoionization line shapes affirms that inelastic electron-cation scattering pathways leading to electron ejection and dissociative recombination proceed through a common continuum.