Computer Simulation of Chemical Dynamics

在理论和计算程序中获得了这笔赠款， 在化学部，长濑教授将使用计算机 模拟研究微观层面的化学动力学。 这些模拟的结果将帮助实验者 估计重要化学反应的速率。 将测试不同的方法来处理零点能 在多原子分子的经典轨道模拟中。 这将部分涉及到与量子动力学的比较， 计算。单分子反应动力学理论将 通过研究（1）波的性质 与特定模式相关的函数和速率常数 （2）分解产物的能量分配; （3）非谐性的处理， 微正则激发的振动/转动耦合 分子。缔合反应的微观性质， 作为能量传递途径和角动量的作用 将进行研究，并将制定一个准确的模型， 缔合速率常数。弥合之间的差距 溶液和气相化学动力学， 将研究溶剂化的反应物。相空间的研究 将执行瓶颈和中心屏障再交叉 SN 2亲核取代反应。

With this grant in the Theoretical and Computational Program of the Chemistry Division, professor Hase will use computer simulation to study chemical dynamics at a microscopic level. The results of these simulations will help experimentalists estimate the rates of important chemical reactions. Different methods will be tested for treating zero point energy in classical trajectory simulations of polyatomic molecules. This will involve, in part, comparisons with quantum dynamical calculations. The theory of unimolecular reaction dynamics will be enhanced by investigating (1) the properties of wave functions and rate constants associated with mode specific decomposition; (2) energy partioning in dissociation products; and (3) the treatment of anharmonicity and vibrational/rotational coupling for microcanonically excited molecules. Microscopic properties of association reactions such as energy transfer pathways and the role of angular momentum will be studied, and an accurate model will be developed for the association rate constant. To bridge the gap between solution and gas-phase chemical kinetics, the association of solvated reactants will be studied. A study of phase space bottlenecks and central barrier recrossing will be performed for SN2 nucleophilic substitution reactions.