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

该提案的目的是实时分析质子耦合电子和电子耦合质子转移反应。我们发展了一种基于海森堡运动方程的量子动力学方法，称为QCD方法和QM/MM分子动力学方法。(1)本文对芘脱氧尿苷在质子和非质子溶剂中进行了QM/MM分子动力学模拟。与溶质分子氢键结合的溶剂分子增强了电子转移反应活性。此外，另一种溶剂分子有助于形成芘和脱氧尿苷基团的桥接结构，从而增强电子转移。(2)为了扩大QCD方法的适用范围，我们发展了基于分布函数的方法和计算量子关联函数的技术。我们将其应用于研究鸟嘌呤-胞嘧啶碱基对质子转移反应的量子同位素效应。(3)我们还对蛋白质环境中的电子耦合质子转移反应进行了第一性原理分析，发现多个质子态在质子跨膜转运过程中起着关键作用。

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.