Molecular Theory and Simulation of Vibrational and Electronic Relaxation and Spectra in Liquid Solution

密歇根大学的Eitan Geva获得了化学理论、模型和计算方法项目的奖励，他开展了理论和计算工具的开发研究，这些工具将提供广泛的非平衡电子、振动和构象过程及其光谱特征的原子详细描述。本研究涉及在极性和质子溶剂中极性和离子物质振动能量弛豫率的最新实验测量背景下的方法开发，醇中羟基拉伸和金属-羰基配合物中羰基拉伸的多维红外光谱以及溶剂对液体溶液中异构化速率的影响。这些研究还涉及与Geva部门的同事实验学家和理论家的合作。振动和电子弛豫是化学中几乎所有重要过程所固有的，包括许多与生物系统相关的过程。非线性光谱技术是研究复杂系统结构和动力学的有力工具。理论方法，如PI和他的研究小组开发的，对于解释这些光谱是必不可少的。这项工作通过培训各级学生、编制课程和传播计算机代码产生了更广泛的影响。

Eitan Geva of the University of Michigan is supported by an award from the Chemical Theory, Models and Computational Methods program to carry out research on the development of theoretical and computational tools that would provide an atomistically detailed description of a wide range of nonequilibrium electronic, vibrational and conformational processes and their spectroscopic signature. This study involves method development in the context of recent experimental measurements of vibrational energy relaxation rates of polar and ionic species in polar and protic solvents, multidimensional infrared spectra of the hydroxyl stretch in alcohols and of the carbonyl stretch in metal-carbonyl complexes and solvent effects on isomerization rates in liquid solution. These studies also involve collaborations with experimentalists and theorists who are colleagues in Geva's department. Vibrational and electronic relaxation is inherent to nearly all processes that are important in chemistry, including many that have relevance to biological systems. Nonlinear optical spectroscopic techniques are powerful probes of the structure and dynamics of complex systems. Theoretical methods, such as those developed by the PI and his research group, are indispensible for interpreting these spectra. The work is having a broader impact through the training of students at all levels, curriculum development and the dissemination of computer codes.