CAREER: Charge-Transfer-to-Solvent Transitions: Experimentaland Theoretical Studies of the Simplest Charge Transfer Reaction

实验物理化学项目支持加州大学洛杉矶分校的Benjamin J. Schwartz对溶剂对化学反应动力学影响的瞬态吸收研究。Schwartz教授将进行飞秒实验，以研究溶剂化卤化物阴离子的电荷转移到溶剂态（CTTS）激发后的动力学。这些实验将测试量子非绝热分子动力学模拟的预测，从而提供有关溶剂在这种最简单的电荷转移反应中的作用的详细信息。平行实验和模拟研究新型溶剂化碱金属阴离子的CTTS跃迁将进一步揭示溶质电子结构在控制电荷转移反应中的作用。这些研究的目的是确定溶剂运动负责溶剂化和溶质电子激发态的非辐射弛豫在溶液中。这些结果将有助于提供一个完整的分子图像，如何在溶剂化动力学和非绝热弛豫之间的相互作用控制溶液中的化学反应性。该职业奖的教育计划强调加强学生的批判性思维能力。此外，还将引入以凝聚态物理化学为重点的新课程。这些研究的目标科学，电子转移和溶剂反应，是化学动力学领域的基础，将带来新的理论和实验相结合的工具，将提供前所未有的细节和审查。鉴于这些过程在自然界和所有凝聚相过程中普遍存在，这些研究将具有深远的意义。

The Experimental Physical Chemistry Program supports Benjamin J. Schwartz of the University of California in Los Angeles in his transient absorption studies of solvent effects on chemical reaction dynamics. Prof. Schwartz will carry out femtosecond experiments in order to examine the dynamics following excitation of the charge-transfer-to-solvent states (CTTS) of solvated halide anions. These experiments will test the predictions of quantum non-adiabatic molecular dynamics simulations, thus providing detailed information about the role of the solvent in this simplest of charge transfer reactions. Parallel experiments and simulations studying the CTTS transitions of novel solvated alkali metal anions will provide further insight into the role of the solute electronic structure in controlling charge transfer reactions. The goal of these studies is to identify the solvent motions responsible for both the solvation and non-radiative relaxation of solute electronic excited states in solution. The results will help to provide a complete molecular picture of how the interplay between solvation dynamics and non-adiabatic relaxation controls chemical reactivity in solution. The education plan of this CAREER award emphasizes the strengthening of critical thinking skills in students. In addition, a new curriculum focusing on condensed-phase physical chemistry will be introduced. The science targeted in these studies, electron transfer and solvent reactions, is fundamental in the area of chemical dynamics, and the novel combined theoretical and experimental tools that will be brought to bear will provide unprecedented detail and scrutiny. Given the ubiquity of these processes in nature and in all condensed phase processes, these studies will have far reaching implications.