Mai Sebastian, Marquetand Philipp, González Leticia
Institute of Theoretical Chemistry, Faculty of Chemistry University of Vienna Vienna Austria.
Wiley Interdiscip Rev Comput Mol Sci. 2018 Nov-Dec;8(6):e1370. doi: 10.1002/wcms.1370. Epub 2018 May 9.
We review the Surface Hopping including ARbitrary Couplings (SHARC) approach for excited-state nonadiabatic dynamics simulations. As a generalization of the popular surface hopping method, SHARC allows simulating the full-dimensional dynamics of molecules including any type of coupling terms beyond nonadiabatic couplings. Examples of these arbitrary couplings include spin-orbit couplings or dipole moment-laser field couplings, such that SHARC can describe ultrafast internal conversion, intersystem crossing, and radiative processes. The key step of the SHARC approach consists of a diagonalization of the Hamiltonian including these couplings, such that the nuclear dynamics is carried out on potential energy surfaces including the effects of the couplings-this is critical in any applications considering, for example, transition metal complexes or strong laser fields. We also give an overview over the new SHARC2.0 dynamics software package, released under the GNU General Public License, which implements the SHARC approach and several analysis tools. The review closes with a brief survey of applications where SHARC was employed to study the nonadiabatic dynamics of a wide range of molecular systems. This article is categorized under: Theoretical and Physical Chemistry > Reaction Dynamics and KineticsSoftware > Simulation MethodsSoftware > Quantum Chemistry.
我们回顾了用于激发态非绝热动力学模拟的包含任意耦合的表面跳跃（SHARC）方法。作为流行的表面跳跃方法的一种推广，SHARC允许模拟分子的全维动力学，包括非绝热耦合之外的任何类型的耦合项。这些任意耦合的例子包括自旋 - 轨道耦合或偶极矩 - 激光场耦合，因此SHARC可以描述超快内转换、系间窜越和辐射过程。SHARC方法的关键步骤包括对包含这些耦合的哈密顿量进行对角化，使得核动力学在包含耦合效应的势能面上进行——这在任何考虑例如过渡金属配合物或强激光场的应用中都是至关重要的。我们还概述了根据GNU通用公共许可证发布的新的SHARC2.0动力学软件包，该软件包实现了SHARC方法以及一些分析工具。综述最后简要介绍了应用SHARC研究各种分子体系非绝热动力学的情况。本文分类如下：理论与物理化学>反应动力学与动力学；软件>模拟方法；软件>量子化学。
