Associative electron detachment: O−+H→OH+e−

Abstract

Associative Electron Detachment processes are important experimental events that can readily be modeled using modern theoretical methods. Experimental methods to date have only allowed one to obtained the relative vibrational distribution of the neutral product molecules. Using a non-Born-Oppenheimer, nonadiabatic, viewpoint that utilizes a fully ab initio approach, we are able to obtain absolute rates (∼104 s for the O−+H system) for transitions from an initial state specified by collision energy and impact parameter, to specific vibrational and rotational states of the neutral OH and a detached electron. The fact that these rates are slow for the O−+H system is due to the large electron affinity of OH (1.8 eV). These rates have an obtuse propensity favoring vibrationally and rotationally hot products. This propensity arises from contributions that are independent and dependent of the angular momentum of the system, an aspect that is of substantial experimental interest. A detailed study of O−+H→OH(V’,J’)+e− is given and generalizations for detachment processes in other systems (F−+H, LiH, BH−) are made.