Dynamics of Electronically Excited States. Models for Chemical Reactivity

实验物理化学计划支持普拉特教授的研究小组继续研究有机大分子的高分辨率电子光谱。从这些研究中获得的信息正在导致重大的定量测试，并在我们对大分子中分子间能量流动的理解方面取得显著的质量改进。在所研究的激发能为3-4 eV，光谱分辨率为几MHz时，被激发电子态的离散自旋-旋转-振动能级被嵌入一个或多个较低电子态的较高密度流形(甚至是准连续谱)中。这些流形之间的耦合允许化学上有趣的过程快速发生；研究试图从本征态分辨光谱中提取关于这些耦合的信息。

The Experimental Physical Chemistry Program supports the research group of Professor Pratt in a continued investigation of high-resolution electronic spectroscopy of large organic molecules. The information gained from these investigations is leading to significant quantitative tests and dramatic qualitative improvements in our understanding of intermolecular energy flow in large molecules. At the studied excitation energies of 3-4 eV and the spectroscopic resolution of a few MHz, the discrete spin-rotation-vibration energy levels of excited electronic states are imbedded in a higher density manifold (or even a quasi-continuum) of levels belonging to one or more lower electronic states. Couplings between these manifolds permit rapid occurrence of chemically interesting processes; the research attempts to extract information about these couplings from eigenstate-resolved spectra.