NSF Young Investigator: Theoretical Studies of Solvent Effects on Solute Reactivity

Susan Tucker获得了美国国家科学基金会理论与计算化学项目的青年研究员资助，研究超临界流体中溶剂对溶质反应性的影响。在超临界状态下，溶剂的性质随着温度和压力的适度变化而急剧变化，但却是连续的。塔克将使用计算机模拟技术，如反应通量分子动力学和伞式采样蒙特卡罗，探索动态和静态溶剂对溶质反应速率影响的微观细节。最初，她将专注于烷基芳基醚的水解，例如苯甲醚，2-甲氧基萘，在超临界水中。这些电荷转移反应的速率对溶剂性质很敏感，因此对理论预测提供了严格的检验。这些反应也经过了广泛的实验研究。此外，将探索广义朗之万方程和caldera - leggett /Zwanzig哈密顿方程中溶剂效应的数学模型，以发展描述溶剂性质变化对溶质反应性影响的新理论。超临界流体在许多工业萃取过程中得到了广泛的应用。它们也被用于环境修复。对在超临界流体溶剂中观察到的独特行为进行统一的理论描述，将对预测热力学条件如何影响超临界流体中的溶质反应性作出重大贡献，并有助于开发利用这些技术上重要的溶剂的工业过程。

Susan Tucker is supported by an NSF Young Investigator Grant from the Theoretical and Computational Chemistry Program to study solvent effects on solute reactivity in supercritical fluids. In the supercritical regime, solvent properties vary dramatically, but continuously, with modest changes in temperature and pressure. Tucker will use computer simulation techniques, such as reactive flux molecular dynamics and umbrella sampling Monte Carlo, to explore the microscopic details of both dynamic and static solvent effects on solute reaction rates. Initially she will focus on the hydrolysis of alkyl aryl ethers, e.g. anisole, 2-methoxynaphthalene, in supercritical water. The rates of these charge transfer reactions are sensitive to solvent properties, and thus provide a stringent test of theoretical predictions. These reactions have also been subjected to extensive experimental studies. In addition, mathematical models for solvent effects within the generalized Langevin equation and the Caldeira-Leggett/Zwanzig Hamiltonian will be explored in order to develop new theories for describing the effect of changing solvent properties on solute reactivity. Supercritical fluids have found widespread application in many industrial extraction processes. They are also being used for environmental remediation. A unified theoretical description of the unique behaviors observed in supercritical fluid solvents would provide a significant contribution to predicting how thermodynamic conditions might affect solute reactivity in supercritical fluids, and aid in the development of industrial processes which make use of these technologically important solvents.