Ultrafast reaction dynamics in condensed phase: Solvent impact on pathways and mechanisms of elementary chemical processes

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The main goal of the project is to develop a powerful framework for ab initio modeling of solvent effects on reaction dynamics starting from a novel quantum-classical methodology recently developed in our group. It has well defined wide applicability limits, and is free from defects inherent in standard hybrid approaches like trajectory surface hopping schemes, mean-field approximations, or the quantum-classical Liouville equation. Towards this end we plan to investigate the accuracy and applicability of a classical mechanics description of reaction coordinates using several reference models, and to develop an effcient numerical implementation of our approach, based on an ab initio molecular dynamics description of classical degrees of freedom. We also plan to achieve non-phenomenologic modeling of reversible geminate recombination reactions starting directly from the Hamiltonian of reactive pair, and to explore the role of coherence and dephasing for the branching ratios in nonadiabatic reactions.