Simulation of Chemical Processes in Condensed Phases Using Hybrid Quantum and Molecular Mechanical Potentials

高嘉礼得到了理论和计算化学计划的资助，继续开发一种混合量子力学和统计力学技术来模拟溶液中和多相催化中的化学过程。研究的目的是获得与实验溶剂化能合理的定量一致。该方法对分子间相互作用的性质提供了新的见解，特别是对凝聚相中的生物化学和材料感兴趣的过程的极化效应的具体贡献。应用包括α-氯醚的热分解和糖基衍生物在有机和水溶液中的模型化合物的水解。这项研究的另一个主要目的是研究与使用沸石催化的甲醇转化为汽油相关的吸附、结合和化学反应。大多数商业上重要的化学过程都发生在溶液中。对溶液中化学反应的计算机模拟为影响反应速率的因素提供了重要的分子水平的见解。然而，许多更有趣的键断裂反应表现出无法用经验势有效建模的量子效应。高的方法涉及使用一种组合的模拟方法，该方法使用蒙特卡罗和分子轨道理论来处理在化学反应中发生变化的量子自由度。

Jiali Gao is supported by a grant from the Theoretical and Computational Chemistry Program to continue his development of a hybrid quantum mechanical and statistical mechanical technique to simulate chemical processes in solution and in heterogeneous catalysis. The objective of the research is to obtain reasonably quantitative agreement with experimental solvation energies. The approach provides new insights on the nature of intermolecular interactions, in particular, specific contributions from the polarization effects for processes of biochemical and materials interest in condensed phases. Applications involve the thermolysis of alpha-chloroethers and hydrolysis of model compounds for glycosyl derivatives in organic and aqueous solutions. Another major thrust of the research is the study of adsorption, binding, and chemical reactions associated with methanol-to-gasoline conversion using zeolite catalysis. Most chemical processes of commercial importance take place in solution. Computer simulations of chemical reactions in solution provide important molecular level insights into the factors that influence reaction rates. Many of the more interesting bond breaking reactions, however, exhibit quantum effects that cannot be modeled effectively using empirical potentials. Gao's approach involves the use of a combined simulation approach which uses Monte Carlo and molecular orbital theory to treat the quantum degrees of freedom undergoing change during the chemical reaction.