Spectroscopy of High Energy Vibrational States

实验物理化学计划支持罗切斯特大学的约翰·S·明特尔继续他对中小分子高振动激发态的结构和动力学的研究。他将用钛宝石激光激发填充激发态，然后使用分子束电共振谱在射频、微波或红外区探测制备态。通过研究具有不同态密度的各种分子，他可以描述分子内振动弛豫开始发生时的高能振动状态。目标是确定(A)包括暗态在内的各种振动模式对激发态波函数的贡献，以及(B)激发态的平衡结构和(C)偶极矩。这种高能分子态的知识将为各种动力学和动力学实验提供重要的基础材料。高能态是一系列化学反应的前驱物质。这些实验旨在提供信息，以最大限度地提高许多动力学和动力学实验的生产率。此外，这里获得的数据将为理论势能面提供严格的测试，而这里获得的高能态知识将允许在未来构建更精确的势能面。最后，为这项工作开发的技术可以应用于许多其他物理化学实验。

The Experimental Physical Chemistry Program supports John S. Muenter of the University of Rochester as he continues his investigations into the structure and dynamics of highly vibrationally excited states of small and medium-sized molecules. He will populate the excited state using Ti:sapphire laser excitation, then probe the prepared state in the radiofrequency, microwave or infrared region using molecular beam electric resonance spectroscopy. By examining a variety of molecules with varying densities of states, he can characterize the high energy vibrational state as intramolecular vibrational relaxation begins to occur. The goals are to determine (a) the contributions of various vibrational modes, including dark states, to the excited state wavefunctions, and the (b) equilibrium structure and (c) dipole moment of the excited state. This knowledge of high energy molecular states will provide important foundation material for a wide variety of kinetics and dynamics experiments. High energy states serve as precursors to a broad range of chemical reactions. These experiments are designed to provide information to maximize the productivity of many kinetics and dynamics experiments. In addition, data obtained here will provide exacting tests of theoretical potential energy surfaces, and the knowledge of high energy states gained here will allow the construction of more accurate potential surfaces in the future. Finally, the techniques developed for this work can be applied to many other experiments in physical chemistry.