Nonradiative deexcitation dynamics of 9H-adenine: An OM2 surface hopping study

The nonradiative relaxation of 9H-adenine was studied at the semiempirical OM2/MR-CI level using the surface-hopping approach. Geometry optimizations of energy minima and conical intersections as well as single-point calculations of excitation energies at critical points were performed to characterize the relevant potential energy surfaces of 9H-adenine and to assess the accuracy of the OM2 results. Surface-hopping calculations were performed to describe the nonradiative dynamics of 9H-adenine after vertical excitation into the optically active state. They showed that the de-excitation process is mainly governed by a two-step relaxation consisting of an ultrashort component and a longer component. These findings compare well with experimental results from time-resolved photoelectron spectroscopy.