Quantum wave packet ab initio molecular dynamics: an approach to study quantum dynamics in large systems.
Quantum wave packet ab initio molecular dynamics: an approach to study quantum dynamics in large systems.
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DOI：
10.1063/1.1871876
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发表时间：
2005-03
期刊：
影响因子：
--
通讯作者：
S. Iyengar;J. Jakowski
中科院分区：
文献类型：
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作者：
S. Iyengar;J. Jakowski
提出了一种有效地进行电子和原子核同时动力学的方法。该方法包括使用离散自由传播子的带状、稀疏和Toeplitz精确表示的量子波包动力学，以及电子和经典核自由度的从头算分子动力学处理。后者可以通过以原子为中心的密度矩阵传播或通过Born-Oppenheimer动力学实现。该方法的两个组成部分，即量子动力学和从头算分子动力学，通过一个依赖于时间的自洽类场耦合过程被利用在一起。通过使用自适应网格来实现优化采样，使得量子波包动力学在计算上具有健壮性。该方法的一个显著特点是精确地处理了重要的量子动力学效应，包括零点效应、隧道效应以及跨势垒反射。电子自由度是在密度泛函理论的精确水平上同时处理的，包括混合或梯度校正近似。给出了质子转移系统的基准计算，并将动力学结果与精确计算进行了比较，以确定该方法的精度。
A methodology to efficiently conduct simultaneous dynamics of electrons and nuclei is presented. The approach involves quantum wave packet dynamics using an accurate banded, sparse and Toeplitz representation for the discrete free propagator, in conjunction with ab initio molecular dynamics treatment of the electronic and classical nuclear degree of freedom. The latter may be achieved either by using atom-centered density-matrix propagation or by using Born-Oppenheimer dynamics. The two components of the methodology, namely, quantum dynamics and ab initio molecular dynamics, are harnessed together using a time-dependent self-consistent field-like coupling procedure. The quantum wave packet dynamics is made computationally robust by using adaptive grids to achieve optimized sampling. One notable feature of the approach is that important quantum dynamical effects including zero-point effects, tunneling, as well as over-barrier reflections are treated accurately. The electronic degrees of freedom are simultaneously handled at accurate levels of density functional theory, including hybrid or gradient corrected approximations. Benchmark calculations are provided for proton transfer systems and the dynamics results are compared with exact calculations to determine the accuracy of the approach.