Ultrafast Measurements on Theoretically Tractable Prototypesfor Polar Solution Chemistry

保罗·芭芭拉教授获得了理论与计算化学项目的资助，从事极性溶剂中超快化学动力学的实验研究。计划在四个特定领域进行研究：1)极性溶剂中小自由基阴离子的振动弛豫研究；2)化学反应过程中反应物电子结构的演变；3)反应体系中质子和溶剂运动的动力学耦合；4)量子溶剂核自由度在电荷转移反应中的作用。由于许多具有重要商业意义的化学反应是在极性溶剂（如水）中发生的，因此了解这些溶剂对反应动力学的影响是很重要的。气相中不存在的溶剂笼效应、振动弛豫和量子力学隧道效应等效应完全支配着凝聚相化学反应。重要的是为模型化学系统发展可靠的理论，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。

Professor Paul Barbara is supported by a grant from the Throretical and Computational Chemistry Program to conduct experimental studies of ultrafast chemical dynamics in polar solvents. Four specific areas of research are planned: 1) an investigation of the vibrational relaxation in small radical anions in polar solvents; 2) the evolution of reactant electronic structure during a chemical reaction; 3) the dynamical coupling of proton and solvent motion in reacting systems; and 4) the role of quantum solvent nuclear degrees of freedom in charge-transfer reactions. %%% 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.