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Toward a Molecular Understanding of Quantum Chemical Dynamics in Solution

溶液中量子化学动力学的分子理解

基本信息

批准号：
9908772
负责人：
Paul Barbara
金额：
$ 28万
依托单位：
University of Texas at Austin
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
1999
资助国家：
美国
起止时间：
1999-08-01 至 2001-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=9908772&HistoricalAwards=false
关键词：
Toward Molecular Understanding Quantum Chemical

项目摘要

Paul Barbara of the University of Texas is supported by a grant from the Theoretical and Computational Chemistry Program to continue his theoretical and experimental research directed at understanding quantum chemical dynamics in solution. Using femtosecond pump-probe optical spectroscopy as an experimental tool Barbara will study: 1) electronically nonadiabatic transitions in symmetric and asymmetric metal-metal intervalence compounds; 2) electronically nonadiabatic transitions in the one and two photon ionization of aqueous iodide solution and the two photon ionization of water; 3) vibrationally nonadiabatic transitions in the photodissociation, recombination, and the vibrational relaxation of small strongly solvated radicals with high frequency vibrations; and 4) the putative long-range coherent electron transfer between metallointercalators in DNA. Theoretical studies are also proposed of current quantum theoretical models for electron transfer and vibrational relaxation.Since many commercially important chemical reactions take place in polar solvents such as water, it is important to understand the influence which such solvents have on the reaction dynamics. A number of effects, such as solvent cage effects, vibrational relaxation and quantum mechanical tunneling, which are not present in the gas phase completely dominate condensed phase chemical reactions. It is important to develop reliable theories for model chemical systems which can then be applied to improving the efficiency of commercially important chemical reactions. The work which is being performed by Barbara provides an important experimental basis for the development of such theories.

德克萨斯大学的Paul Barbara得到了理论和计算化学项目的资助，继续他的理论和实验研究，旨在了解溶液中的量子化学动力学。Barbara将利用飞秒泵浦-探测光谱技术研究：1）对称和非对称金属-金属间价化合物的电子非绝热跃迁，2）碘水溶液的单光子和双光子电离以及水的双光子电离的电子非绝热跃迁; 3）在具有高频振动的小的强溶剂化自由基的光解离、复合和振动弛豫中的振动非绝热跃迁;（4）DNA中金属嵌入剂之间的长程相干电子转移。由于许多商业上重要的化学反应都发生在极性溶剂如水中，因此了解这些溶剂对反应动力学的影响是很重要的。一些效应，如溶剂笼效应，振动弛豫和量子力学隧道，这是不存在于气相中完全支配凝聚相化学反应。重要的是发展可靠的理论模型化学系统，然后可以应用于提高商业上重要的化学反应的效率。芭芭拉正在进行的工作为这些理论的发展提供了重要的实验基础。