Semiclassical molecular dynamics simulations of excited state double-proton transfer in 7-azaindole dimers

Abstract

An ab initio excited state potential energy surface is constructed for describing excited state double proton transfer in the tautomerization reaction of photo-excited 7-azaindole dimers, and the ultrafast dynamics is simulated using the semiclassical (SC) initial value representation (IVR). The potential energy surface, determined in a reduced dimensionality, is obtained at the CIS level of quantum chemistry, and an approximate version of the SC-IVR approach is introduced which scales linearly with the number of degrees of freedom of the molecular system. The accuracy of this approximate SC-IVR approach is verified by comparing our semiclassical results with full quantum mechanical calculations. We find that proton transfer usually occurs during the first intermonomer symmetric-stretch vibration, about 100 fs after photoexcitation of the system, and produces an initial 15 percent population decay of the reactant base-pair, which is significantly reduced by isotopic substitution.