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

密歇根大学的Eitan Geva得到了化学理论、模型和计算方法计划颁发的奖项的支持，该计划旨在开展理论和计算工具开发的研究，这些工具将提供对广泛的非平衡电子、振动和构象过程及其光谱特征的原子学详细描述。这项研究包括在最近的实验测量中极性和离子物种在极性和质子性溶剂中的振动能弛豫速率，醇中羟基伸展和金属-羰基络合物中的羰基伸展的多维红外光谱，以及溶剂对液体中异构化速率的影响的方法发展。这些研究还包括与Geva部门的同事、实验学家和理论家的合作。振动和电子松弛是几乎所有化学中重要的过程所固有的，包括许多与生物系统相关的过程。非线性光学光谱技术是研究复杂系统结构和动力学的有力探针。理论方法，如PI和他的研究小组开发的方法，对于解释这些光谱是必不可少的。通过培训各级学生、编制课程和传播计算机代码，这项工作正在产生更广泛的影响。

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.