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

在该奖项中，由化学部实验物理化学计划资助，德克萨斯A M大学的John Bevan和Robert Lucchese及其学生将继续他们的研究，以开发基于实验研究和量子化学计算相结合的非共价相互作用的准确通用模型。 最近在红外和亚毫米/太赫兹光谱区域的技术进步提供了独特的机会，选择典型的非共价相互作用的综合实验研究。 调查将集中在研究基态同位素异构化，这是一种异常的氘同位素效应，开发一种超灵敏的腔增强检测方法，用于使用高分辨率太赫兹光谱研究负离子团簇，并通过变形方法对分子内和分子间模式的耦合进行建模。实验研究将允许所选择的系统具有很高的精度和基准数据生成高度准确的振动完整的半经验变形的潜力的表征。这种方法的主要优点是，它们为原型的非键相互作用生成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特性，并以前所未有的准确度预测特性。最终，这些方法应导致更广泛的应用，包括预测分子间的相互作用在较大的集群和模型系统不太服从详细的光谱研究。这些结果将为理解包括蛋白质和其他生物分子在内的较大物种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中的问题。该项目支持的学生将接受最先进的实验和理论技术的培训，包括通过国际合作获得职业发展的机会。

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.