Solving the time-dependent Schrödinger equation for nuclear motion in one step: direct dynamics of non-adiabatic systems
Solving the time-dependent Schrödinger equation for nuclear motion in one step: direct dynamics of non-adiabatic systems
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DOI：
10.1080/00268970802172503
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发表时间：
2008-08
影响因子：
1.7
通讯作者：
G. Worth;M. Robb;B. Lasorne
中科院分区：
文献类型：
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作者：
G. Worth;M. Robb;B. Lasorne
本文综述了直接动力学方法在非绝热光化学中的应用。圆锥交叉点在其中起着重要作用的系统。直接动力学模拟使用电子结构计算，以获得势能面，只有当它是需要的“在飞行中”。这与传统方法相反，传统方法需要在执行模拟之前将曲面全局称为解析函数。比较了轨道表面跳跃法（TSH）、从头算多重生成法（AIMS）和变分多组态高斯波包法（vMCG）三种主要方法的性质和能力，并给出了计算结果。TSH是最接近经典动力学的，是最简单的实现，但很难收敛，甚至不总是准确的。AIMS更严格地解决了依赖于时间的薛定谔方程，但由于其基函数遵循经典轨迹，因此收敛性又很差。vMCG更难实现，但它的基函数不遵循经典轨迹，收敛速度更快。
A review of direct dynamics methods is given, focusing on their application to non-adiabatic photochemistry–i.e. systems in which a conical intersection plays an important role. Direct dynamics simulations use electronic structure calculations to obtain the potential energy surface only as it is required ‘on-the-fly’. This is in contrast to traditional methods that require the surface to be globally known as an analytic function before a simulation can be performed. The properties and abilities, with descriptions of calculations made, of the three main methods are compared: trajectory surface hopping (TSH), ab initio multiple spawning (AIMS), and variational multi-configuration Gaussian wavepackets (vMCG). TSH is the closest to classical dynamics, is the simplest to implement, but is hard to converge, and even then not always accurate. AIMS solves the time-dependent Schrödinger more rigorously, but as its basis functions follow classical trajectories again suffers from poor convergence. vMCG is harder to implement, but its basis functions do not follow classical trajectories and it converges much faster.