Simulation of the π → π* photodynamics of azobenzene: Decoherence and solvent effects

We present surface hopping simulations of the photodynamics of azobenzene excited in the pi -> pi* band, in vacuo and in two solvents of different viscosity. We apply the overlap based quantum decoherence correction (ODC) previously devised by our group, and we propose a criterium to calibrate the ODC when no experimental or theoretical benchmarks are available. We show that decoherence has an important effect on the excited state decay. Solvation also affects the lifetimes, as well as the quantum yields and important details of the reaction mechanism. (C) 2014 Elsevier B.V. All rights reserved.