Dynamics of Photoisomerization and Nonadiabatic Relaxation Processes

约翰·弗雷德里克得到了理论和计算化学计划的资助，继续他对光异构化动力学和非绝热弛豫过程的研究。这项工作的目的是为己三烯和辛四烯体系中光诱导过程的电子和振动动力学建立详细的模型。我们将结合高水平从头计算和光谱数据，得到这些系统最低三个单重态的定量精确势能面以及它们之间的非绝热耦合。我们将用准经典和量子动力学来研究这些体系中的超快内转化和异构化过程。关于这些系统的光化学和光物理的一些具体问题将被阐明。在许多自然过程中，如视觉和光合作用，以及具有导电和光致变色性能的有机材料的开发中，多烯的光化学是非常重要的。拟议的工作在为这些现象提供分子水平的解释方面有可能产生重大的科学影响。

John Frederick is supported by a grant from the Theoretical and Computational Chemistry Program to continue his studies of the dynamics of photoisomerization and nonadiabatic relaxation processes. The objective of this work is to develop detailed models for the electronic and vibrational dynamics of the photoinduced processes in the hexatriene and octatetraene systems. Quantitatively accurate potential energy surfaces for the lowest three singlet states of these systems and the nonadiabatic coupling between them will be derived using a combination of high-level ab initio calculations and spectroscopic data. Ultrafast internal conversion and isomerization processes in these systems will be studied using both quasiclassical and quantum dynamics. A number of specific questions regarding the photochemistry and photophysics of these systems will be elucidated. The photochemistry of polyenes is of central importance in a number of natural processes, such as vision and photosynthesis, and in the development of organic materials with conducting and photochromic properties. The proposed work has a potential for significant scientific impact in providing a molecular level interpretation of these phenomena.