Theoretical Studies of Reactive Molecular Processes

Yngve Ohrn和Erik Deumens得到了理论和计算化学计划的资助，他们发展了电子核动力学，这是一种寻找随时间变化的薛定谔方程近似解的一般方法。通过以非玻恩-奥本海默方式求解该方程，即将原子核和电子置于同等地位，他们的方法避免了传统方法所需要的大量势能表面点和非绝热耦合项的计算。代价是要处理的粒子数量增加，但由于计算能力的进步，这种方法在经济上具有竞争力。应用包括抽氢反应和多原子分子阳离子的解离重组。基本化学反应是涉及参与的电子和原子核的动力学事件。这种动力学在最基本的层面上是由时变薛定谔方程描述的。求解该方程的一般方法将得到难以通过实验得到的基本化学反应的反应速率。

Yngve Ohrn and Erik Deumens are supported by a grant from the Theoretical and Computational Chemistry Program to develop electron nuclear dynamics, a general approach to find approximate solutions to the time-dependent Schrodinger equation. By solving this equation in a non-Born-Oppenheimer way, that is, by placing the nuclei and the electrons on an equal footing, their method avoids the extensive computation of potential energy surface points and nonadiabatic coupling terms required by traditional approaches. The trade-off is an increase in the number of particles to be treated, but due to advances in computational power, this method is economically competitive. Applications include hydrogen abstraction reactions and dissociative recombinations of polyatomic molecular cations. Elementary chemical reations are dynamical events involving the participating electrons and atomic nuclei. Such dynamics are described at the most fundamental level by the time-dependent Schrodinger equation. A general approach to solving this equation will yield reaction rates for elementary chemical reactions which are difficult to obtain experimentally.