Molecular Dynamics Simulation of Chemical Reactions at Liquid Interfaces

Ilan Benjamin，加州大学圣克鲁斯分校，由理论和计算化学项目资助，继续他在液体界面化学反应分子动力学模拟研究方面的理论工作。平衡和非平衡分子动力学计算机模拟以及连续静电和扩散模型将用于研究界面的独特特性如何影响几种化学反应系统的行为。要研究的问题包括：1)溶质调节和水/液/气界面的反应；2)液体混合物液/气界面处的扭扭-反式异构化反应；3)大疏水离子在液/液界面上的转移；4)电化学液/液界面的离子配对。化学领域的一个重要挑战是在分子水平上理解溶剂介质对化学反应的影响。大多数具有重要商业意义的化学反应都是在溶液中发生的，而且经常在催化剂的存在下进行。近年来，一些凝聚相实验技术的发展，如飞秒时间分辨光谱和非线性光谱，为研究液-气和液-液界面的化学提供了新的信息。本雅明的理论工作将有助于在分子水平上解释这一新的实验信息。

Ilan Benjamin, University of California Santa Cruz, is funded by a grant from the Theoretical and Computational Chemistry Program to continue his theoretical work in the study of molecular dynamic simulations of chemical reactions at liquid interfaces. Equilibrium and non-equilibrium molecular dynamics computer simulations and continuum electrostatic and diffusion models will be used to investigate how the unique characteristics of the interface affect the behavior of several chemically reactive systems. The problems to be studied include: 1) solute accommodation and reactions at the water liquid/vapor interface; 2) gauche-trans isomerization reactions at the liquid/vapor interface of liquid mixtures; 3) transfer of large hydrophobic ions across the liquid/liquid interface; and 4) ion pairing at the electrochemical liquid/liquid interface. An important challenge in the field of chemistry is to understand at the molecular level the effect of the solvent medium on chemical reactions. Most chemical reactions of commercial importance occur in solution and are frequently carried out in the presence of a catalyst. Recent development of a number of condensed phase experimental techniques, such as femtosecond time-resolved spectroscopy and non-linear spectroscopy, have provided new information on chemistry at the liquid-vapor and liquid-liquid interfaces. Benjamin's theoretical work will help to provide a molecular level interpretation of this new experimental information.