A scheme to interpolate potential energy surfaces and derivative coupling vectors without performing a global diabatization
A scheme to interpolate potential energy surfaces and derivative coupling vectors without performing a global diabatization
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DOI：
10.1063/1.3660686
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发表时间：
2011-12-14
影响因子：
4.4
通讯作者：
Martinez, Todd J.
中科院分区：
文献类型：
--
作者：
Evenhuis, Christian;Martinez, Todd J.
非绝热分子动力学的模拟需要描述多个电子态势能面及其耦合。从头算分子动力学方法提供了一个有吸引力的途径来实现这一点，但在巨大的计算费用。插值方法提供了一种可能的途径，以实现灵活的描述势能面和他们的耦合，以减少费用。以前开发的方法的基础上修改谢泼德插值需要全球糖尿病，这可能是有问题的。在这里，我们广泛地修改了以前的方法，避免了全球糖尿病的需要。由此产生的插值势只提供绝热能量、梯度和导数耦合。这种新的插值方法已被集成与从头算多次产卵方法，它已被严格验证对直接动力学。它示出，至少对于小分子，构建一个内插PES可以更有效地比执行直接动力学测量的从头计算所需的一个给定的精度的总数。(C)2011年美国物理学会。[doi：10.1063/1.3660686]
Simulation of non-adiabatic molecular dynamics requires the description of multiple electronic state potential energy surfaces and their couplings. Ab initio molecular dynamics approaches provide an attractive avenue to accomplish this, but at great computational expense. Interpolation approaches provide a possible route to achieve flexible descriptions of the potential energy surfaces and their couplings at reduced expense. A previously developed approach based on modified Shepard interpolation required global diabatization, which can be problematic. Here, we extensively revise this previous approach, avoiding the need for global diabatization. The resulting interpolated potentials provide only adiabatic energies, gradients, and derivative couplings. This new interpolation approach has been integrated with the ab initio multiple spawning method and it has been rigorously validated against direct dynamics. It is shown that, at least for small molecules, constructing an interpolated PES can be more efficient than performing direct dynamics as measured by the total number of ab initio calculations that are required for a given accuracy. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3660686]