First Principles Quantum Molecular Dynamics: Density Matrix Theory and Computational Aspects

佛罗里达大学的David Micha受到理论和计算化学计划的支持，致力于探索分子相互作用的第一原理量子动力学的密度矩阵方法。新技术将把依赖时间的哈特里-福克理论与原子核运动的动能方法结合起来。将开发计算算法来计算电子态布居的时间演化、自旋-轨道重新耦合和态到态截面。应用包括气相碰撞和固体表面电子重排的飞秒动力学和光谱。这一理论旨在提供新的见解、概念和预测计算工具来处理分子中碰撞诱导和光诱导的电子跃迁。它的计算实现产生了电子势能、它们的耦合以及用于研究动力学现象的跃迁偶极子。它将有助于解释最近涉及飞秒化学、瞬变物种的受激发射和溶剂化物种的光谱的新实验。

David Micha of the University of Florida is supported by the Theoretical and Computational Chemistry Program to pursue density matrix approaches to first principle quantum dynamics of molecular interactions. New techniques will combine time-dependent Hartree-Fock theory with eikonal methods for nuclear motion. Computational algorithms will be developed to calculate time-evolution of electronic state populations, spin-orbit recoupling, and state-to-state cross sections. Applications include femtosecond dynamics and spectra of electronic rearrangement in gas-phase collisions and at solid surfaces. This theory aims to provide new insight, concepts, and predictive computational tools to deal with collision-induced and photoinduced electronic transitions in molecules. Its computational implementation generates electronic potential energies, their couplings, and transition dipoles for studies of dynamical phenomena. It will aid in the interpretation of recent novel experiments involving femtosecond chemistry, stimulated emission of transient species, and spectroscopy of solvated species.