Spectroscopic and Computational Investigations of Fundamental Characteristics in Non-covalent Interactions

该奖项由化学部门的实验物理化学项目资助，德克萨斯农工大学的John Bevan和Robert Lucchese以及他们的学生将继续他们的研究，在实验研究和量子化学计算的基础上，开发精确的非共价相互作用的广义模型。红外和亚毫米/太赫兹光谱区域的最新技术进步为选定的原型非共价相互作用的综合实验研究提供了独特的机会。研究将集中在基态同位素异构化（一种异常氘同位素效应）的研究，利用高分辨率太赫兹光谱开发用于研究负离子簇的超灵敏腔增强检测方法，以及通过变形方法模拟分子内和分子间模式的耦合。实验研究将允许对所选系统进行高精度的表征，并为产生高精度的振动完全半经验变形势提供基准数据。这些方法的主要优点是，它们为原型非键相互作用生成了全面的微观半经验模型，可以揭示与非共价相互作用相关的基本新性质，并以前所未有的精度预测性质。最终，这些方法将导致更广泛的应用，包括预测更大的团簇和模型系统中的分子间相互作用，这些模型系统不太适合进行详细的光谱研究。这些结果将为理解大型物种（包括蛋白质和其他生物分子）的结构和内部运动提供基准，并有助于解决大气化学、生物化学、地球化学和材料工程方面的问题。该项目支持的学生将接受最先进的实验和理论技术培训，并通过国际合作获得职业发展机会。

In this award, funded by the Experimental Physical Chemistry Program of the Chemistry Division, John Bevan and Robert Lucchese of Texas A&M University and their students will continue their research to develop accurate generalized models for non-covalent interactions based on a combination of experimental investigation and quantum chemical calculations. Recent technological advances in the infrared and submillimeter/terahertz spectral regions provide unique opportunities for comprehensive experimental investigations of selected prototypical non-covalent interactions. Investigations will focus on studies of ground state isotopic isomerization which is an anomalous deuterium isotope effect, development of an ultra-sensitive cavity-enhanced detection method for investigation of negative ion clusters using high resolution terahertz spectroscopy, and modeling of coupling of intra- and intermolecular modes through morphing approaches. The experimental studies will permit characterization of the selected systems with great precision and provide benchmark data for generating highly accurate vibrationally complete semi-empirical morphed potentials. The principle advantage of such methods is that they generate comprehensive microscopic semi-empirical models for prototypical, non-bonded interactions that can reveal fundamental new properties associated with non-covalent interactions as well as predicting properties with unprecedented accuracy. Ultimately, these approaches should lead to more generalized applications, including the prediction of the intermolecular interactions in larger clusters and model systems less amenable to detailed spectroscopic studies. The results will provide benchmarks for understanding the structure and internal motions of larger species, including proteins and other biological molecules, as well as contributing to the solutions of problems in atmospheric chemistry, biochemistry, geochemistry, and materials engineering. Students supported in this project will receive training in both state-of-the-art experimental and theoretical techniques including opportunities for career advancement through international collaborations.