Ultrafast Transient Raman Investigations of Dynamic Solvent Effects on Chemical Reactivity in Supercritical Fluids

约翰B博士。霍普金斯和卡尔F.克诺夫基金会得到了一笔赠款的支持， 从理论和计算化学计划， 进行超快瞬态拉曼光谱研究 在超临界流体中发生的反应。 的目标 本研究旨在了解溶剂在 凝聚相化学反应 本研究的主要目的是研究溶剂 原子临界点附近的化学动力学效应 和小的多原子溶剂。 霍普金斯和克诺夫医生 试图表征团簇中的局部溶剂密度 周围无限稀释的溶质分子， 临界点，直接测量密度依赖性 双原子溶质分子的振动能弛豫。 他们还将研究局部溶剂密度的影响 用超快激光研究化学动力学 光解和成对复合反应。 直接 真实的时间调查将侧重于了解 1）溶剂团簇和动态密度涨落，2）货车 3）在确定的过程中的能量转移 不同流体密度下的反应性。

Drs. John B. Hopkins and Carl F. Knopf are supported by a grant from the Theoretical and Computational Chemistry Program to perform ultrafast transient Raman spectroscopic investigations of reactions occuring in supercritical fluids. The goal of this research is to understand the role which solvent plays in condensed phase chemical reactions. The main thrust of the research is to investigate solvent effects on chemical dynamics near the critical point of atomic and small polyatomic solvents. Drs. Hopkins and Knopf will attempt to characterize the local solvent density in clusters surrounding infinitely dilute solute molecules near the critical point by directly measuring the density dependence of vibrational energy relaxation in diatomic solute molecules. They will also investigate the effect of local solvent density on chemical dynamics using ultrafast laser studies of photodissociation and geminate recombination reactions. Direct real time investigations will focus on understanding the role of 1) solvent clusters and dynamic density fluctuations, 2) van der Waals complexes, and 3) energy transfer in determining reactivity at different fluid densities.