Simulation of photo-excited adenine in water with a hierarchy of equations of motion approach

Abstract

We present a theoretical method to simulate the electronic dynamics and two-dimensional ultraviolet spectra of the nucleobase adenine in water. The method is an extension of the hierarchy of equation of motion approach to treat a model with one or more conical intersections. The application to adenine shows that a two-level model with a direct conical intersection between the optically bright state and the ground state, generating a hot ground state, is not consistent with experimental observations. This supports a three-level model for the decay of electronically excited adenine in water as was previously proposed in [Prokhorenko et al., J. Phys. Chem. Lett. 7, 4445 (2016)]