Ab initio dynamics with wave-packets and density matrices
Ab initio dynamics with wave-packets and density matrices
复制标题
波包和密度矩阵的从头算动力学
DOI：
10.1007/s00214-005-0010-3
复制
发表时间：
2006
影响因子：
1.7
通讯作者：
S. Iyengar
中科院分区：
文献类型：
--
作者：
S. Iyengar
有效的方法进行电子和原子核的同时动力学进行了讨论。特别是，注意力是针对最近的发展，结合量子动力学从头算分子动力学。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，利用一个依赖于时间的自洽场耦合过程。一种方法来进行量子动力学使用一个精确的带状，稀疏和Toeplitz表示的离散自由传播子突出与适当的审查其他相关的方法。该方法的一个显著特点是，所有重要的量子动力学效应，包括零点效应，隧穿以及过势垒反射被精确处理。还讨论了提高量子动力学效率的计算方法。有许多方法可以同时进行从头算分子动力学（如Born-Oppenheimer动力学和扩展的拉格朗日动力学，Car-Parrinello动力学是后者的一个主要例子）;我们的主要焦点仍然是原子中心的密度矩阵传播和Born-Oppenheimer动力学。电子自由度的处理在准确的水平密度泛函理论，使用混合或梯度校正近似。基准计算提供了一个原型质子转移系统。未来的概括和目标进行了讨论。
Efficient methodologies to conduct simultaneous dynamics of electrons and nuclei are discussed. Particularly, attention is directed to a recent development that combines quantum dynamics with ab initio molecular 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. An approach to conduct quantum dynamics using an accurate banded, sparse and Toeplitz representation for the discrete free propagator is highlighted with suitable review of other related approaches. One notable feature of the method is that all important quantum dynamical effects including zero-point effects, tunneling as well as over-barrier reflections are accurately treated. Computational methodologies for improved efficiency of the quantum dynamics are also discussed. There exists a number of ways to carry out simultaneous ab initio molecular dynamics (such as Born–Oppenheimer dynamics and extended Lagrangian dynamics, Car–Parrinello dynamics being a prime example of the latter); our prime focus remains on atom-centered density-matrix propagation and Born–Oppenheimer dynamics. The electronic degrees of freedom are handled at accurate levels of density functional theory, using hybrid or gradient corrected approximations. Benchmark calculations are provided for a prototypical proton transfer system. Future generalizations and goals are discussed.