Theoretical and Computational Studies of Multiple Charge Transfer Reactions in the Condensed Phase

Sharon Hammes-Schiffer得到了理论和计算化学计划的支持，致力于研究多重电荷转移反应，包括多重质子转移和质子耦合电子转移。这个项目的主要目标是阐明凝聚相中多个电荷转移反应的基本原理。将采取两种相辅相成的办法来实现这一目标。在第一种方法中，使用混合量子/经典分子动力学方法，将溶剂表示为经典处理的显式分子，而转移质子和活性电子则用量子力学处理。在第二种方法中，基于多态连续介质理论，将溶剂表示为介电连续介质，并对转移的质子和活泼电子进行量子力学处理。这两种方法都将通过对模型系统的应用来开发和测试。这种理论和计算方法的发展以及随后在化学和生物相关系统中的应用相结合，将提供对多重电荷转移反应的基本原理的洞察。这样的反应在质子线(质子沿水分子链运输)、不对称盐桥和对新陈代谢至关重要的酶反应中都是重要的。

Sharon Hammes-Schiffer is supported by the Theoretical and Computational Chemistry Program to pursue investigations of multiple charge transfer reactions, including multiple proton transfer and proton-coupled electron transfer. The broad goal of this project is to elucidate the fundamental principles of multiple charge transfer reactions in the condensed phase. Two complementary approaches will be implemented to accomplish this goal. In the first approach, using mixed quantum/classical molecular dynamics methods, the solvent is represented as explicit molecules treated classically, while transferring protons and active electrons are treated quantum mechanically. In the second approach, based on multistate continuum theory, the solvent is represented as a dielectric continuum and the transferring protons and active electrons are treated quantum mechanically. Both approaches will be developed and tested by applications to model systems.This combination of the development of theoretical and computational methodology and subsequent application to chemically and biologically relevant systems will provide insight into the fundamental principles of multiple charge transfer reactions. Such reactions are important in proton wires (proton transport along chains of water molecules), asymmetric salt bridges, and enzyme reactions vital to metabolism.