Real-time analyses of proton-coupled electron transfer reactions : Quantal cumulant dynamics

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The aim of the proposal is a real-time analysis of proton-coupled electron and electron-coupled proton transfer reactions. We develop a novel quantum dynamics method based on Heisenberg' equation of the motion, which is referred as QCD method, and QM/MM molecular dynamics methods. (1) We perform QM/MM molecular dynamics simulation of pyrene-deoxyuridine in protonic and non-protonic solvent environment. Solvent molecules, which are hydrogen-bonded to a solute molecule, enhance the electron transfer reaction activity. Moreover, another solvent molecule assist to form a bridged structure of pyrene and deoxyuridine groups that results in the enhancement of the electron transfer. (2) In order to enlarge the applicability of the QCD method, we develop the distribution function based method and the techniques for the calculation of quantum correlation functions. We applied it to investigate quantum isotope effects on the proton transfer reactions in a guanine-cytosine base pair. (3) We also performed the first principle analysis of electron-coupled proton transfer reaction in protein environment and found that multiple protonic states play a key role in proton transport process across membrane proteins.