Electron detachment dynamics of the microsolvated benzophenoneradical anion: A full dimensional direct ab-initio trajectory approach

Abstract

Electron detachment dynamics of the benzophenone anion–water complex Bp⁻(H₂O) have been investigated by means of full dimensional direct ab-initio trajectory calculation. The structural relaxation process of the neutral complex Bp(H₂O) following the vertical electron detachment of Bp⁻(H₂O), which is expressed by [Bp(H₂O)]_ver → [Bp(H₂O)]_solv, was calculated by the direct ab-initio trajectory calculations, where [Bp(H₂O)]_ver and [Bp(H₂O)]_solv mean the Bp(H₂O) neutral complex having a structure at vertical electron detachment point from the Bp⁻(H₂O) anion complex and a relaxation structure of Bp(H₂O), respectively. From the dynamics calculations, it was found that the solvation structure of Bp(H₂O) is drastically changed to [Bp(H₂O)]_solv after the electron detachment of Bp⁻(H₂O). According to the structural relaxation including the solvent re-orientation around the benzophenone, the excitation energies for both nπ* and ππ* transitions were blue-shifted as a function of time. The mechanism of the electron detachment process was discussed on the basis of theoretical results.