Photodissociation of phenol via nonadiabatic tunneling: Comparison of two ab initio based potential energy surfaces

摘要

The nonadiabatic tunneling-facilitated photodissociation of phenol is investigated using a reduceddimensional quantum model on two ab initio-based coupled potential energy surfaces (PESs). Although dynamics occurs largely on the lower adiabat, the proximity to a conical intersection between the S-1 and S-2 states requires the inclusion of both the geometric phase (GP) and diagonal BornOppenheimer correction (DBOC). The lifetime of the lowest-lying vibronic state is computed using the diabatic and various adiabatic models. The GP and DBOC terms are found to be essential on one set of PESs, but have a small impact on the other. (C) 2017 Elsevier B. V. All rights reserved.