羰基化合物激发态势能面交叉动力学的共振拉曼光谱和CASSCF计算研究

项目名称： 羰基化合物激发态势能面交叉动力学的共振拉曼光谱和CASSCF计算研究

项目编号： No.21473163

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 郑旭明

作者单位： 浙江理工大学

项目金额： 90万元

中文摘要： 激发态势能面交叉动力学在光化学反应中起着举足轻重的作用。Franck-Condon(FC)区域势能面锥形交叉点附近的内转换过程极其快速，现有超快实验技术难以直接观测。本项目采用共振拉曼光谱技术和CASSCF等计算方法，开展羰基化合物激发态势能面锥形交叉动力学研究。期望通过不饱和烯醛(酮)、核酸碱基、芳香醛(酮)及其衍生物等一系列分子体系的研究，找到与各类势能面锥形交叉动力学相关的特征反应坐标(拉曼标记)，探明羰基化合物FC区域各类势能面交叉动力学的取代基效应和溶剂效应规律。探索不同取代基(NH2、CN等)引发激发态分子内质子转移和电荷转移反应通道对FC区域势能面锥形交叉通道的调控途径。采用低温基质隔离-共振拉曼光谱技术，研究基质隔离条件下羰基化合物激发态结构动力学，发现溶剂性质影响羰基化合物FC区域势能面交叉动力学的微观机制。本研究将为势能面交叉动力学研究提供一条独途径。

中文关键词： 动力学；激发态；超快光谱；光化学；计算化学

英文摘要： The dynamics of the excited state potential energy surface (PES) crossing plays an important role in the photochemical reactions. In the vicinity of a conical intersection in the Franck-Condon region, the internal conversion (IC) process is extremely fast so that it is difficult to detect directly by current ultrafast spectroscopic techniques. In this proposal, the resonance Raman spectroscopic in conjunction with CASSCF computational method is employed to study the excited state PES crossing dynamics of the carbonyl compounds. Through extensive study of the selected molecule systems including unsaturated aldehydes (ketones), nucleobases, and aromatic aldehydes (ketones), we expect to discover the characteristic coordinates (Raman marks) that label the dynamics of the conical intersection between the interested PES, and to reveal the regularities in the influences of the substituents and the solvents on the excited state PES crossing dynamics in the Franck-Condon region of nucleobases. We explore the regularities in the effect of the substituent-induced excited state intramolecular proton-transfer and electron transfer reaction channels on the FC region conical intersectional dynamics of the carbonyl coumpounds. Based on the exploratory research on the excited state structural dynamics of the carbonyl compounds through the use of matrix-isolation combined resonance Raman technique under cryogenic condition, we aim to reveal the mechanism that solvents affect the PES crossing dynamics of carbonyl compounds in the Franck-Condon region on the molecular-level. Our studies will provide a unique way in the investigation of the PES crossing dynamics in the photochemistry.

英文关键词： dynamics;excited state;ultrafast spectroscopy;photochemistry;computational chemistry