Development of Semiclassical Surface Hopping Methods for Systems Undergoing Quantum Transitions

杜兰大学的Michael F.Herman得到了理论和计算化学计划的支持，继续设计精确的半经典方法来研究经历量子跃迁的复杂系统。这些方法正在提高半经典格式的数值效率，这使得它们可以应用到更现实的物理系统中。正在进行的发展包括通过为其实施提供坚实的理论基础来扩展表面跳跃方法家族，开发基于经典分子动力学的初值表示(IVR)，以及描绘近似的层次以创造机会应用于广泛的问题。这些方法将使研究更大、更复杂的系统具有更高的准确性、效率和可靠性。应用包括液体中分子振动能弛豫的模型，以及凝聚相中电子从施主系统到受主系统的转移。这项工作在培训本科生、研究生和博士后助理教授化学物理理论和计算方法方面产生了更广泛的影响。这项工作中开发的方法提供了多种工具，这些工具将在各种领域得到应用。

Michael F. Herman of Tulane University is supported by the Theoretical and Computational Chemistry Program to continue work in designing accurate semiclassical methods to study complex systems undergoing quantum transitions. These methods are improving the numerical efficiency of semiclassical schemes, which is allowing them to be applied to more realistic physical systems. Developments underway include extending the family of surface hopping methods by providing a solid theoretical basis for their implementation, developing an Initial Value Representation (IVR) based on classical molecular dynamics, and delineating a hierarchy of approximations to create opportunities for applications to a broad range of problems. These methods will allow studies of more larger and more complex systems with greater accuracy, efficiency and reliability. Applications include models of the relaxation of vibrational energy of molecules in liquids, and electron transfer from a donor system to an acceptor system in the condensed phase. This work is having a broader impact in training undergraduates, graduate students and postdoctoral associates in chemical physics theory and computational methods. The methods developed in this work are providing versatile tools that will find application in a variety of fields.