Experimental and Theoretical Studies of Model Chemical Reactions Under Variable Pressure and Temperature

在化学学部实验物理化学项目的这个项目中，Ben-Amotz将使用压力和温度相关的光谱学研究以及理论建模来研究溶质-溶剂相互作用对化学反应的影响。解离、异构化和离子配对模型反应将被研究，模型反应的平衡常数的变化将在有机溶剂以及超临界氩、氙和水中使用高压拉曼、FTIR和紫外/可见光谱在金刚石顶柱超临界流体压力电池中测量。研究结果将用于测试从液体微扰理论中导出的理论模型，该模型使用第一原理方法和半经验摄动硬流体（PHF）模型。预测结果和实验结果将在液体和超临界流体溶剂的宽压力和温度范围内进行比较。使用预测模型来计算系统性能的价值，特别是在极端温度或压力条件下的系统，已经得到工程师们的广泛认可。这些研究将有助于我们预测在日益极端和复杂的凝聚相条件下的化学反应平衡。这项工作的结果可能对工业化学合成，废物回收和分离技术具有重要意义。

In this project in the Experimental Physical Chemistry Program of the Chemistry Division, Ben-Amotz will study the influence of solute-solvent interactions on chemical reactions using pressure- and temperature-dependent optical spectroscopic studies as well as theoretical modeling. Dissociation, isomerization, and ion-pairing model reactions will be studied, and changes in the equilibrium constants for model reactions will be measured in organic solvents as well as in supercritical argon, xenon, and water using high-pressure Raman, FTIR, and UV/visible spectroscopies in diamond anvil supercritical fluid pressure cells. The results will be used to test theoretical models derived from liquid perturbation theory using both a first-principles approach as well as a semi-empirical perturbed hard fluid (PHF) model. Predicted and experimental results will be compared over a wide pressure and temperature range in both liquid and supercritical fluid solvents. The value of using predictive models to calculate properties of systems, especially those under extreme conditions of temperature or pressure, has become widely recognized by engineers. These studies will contribute to our ability to predict chemical reaction equilibria under increasingly extreme and complex condensed phase conditions. The results of this work are likely to be important to industrial chemical synthesis, waste recovery, and separation technologies.