Department of Chemistry and Centre for Scientific Computing, University of Warwick, Coventry CV4 7AL, United Kingdom.
J Chem Phys. 2018 Apr 7;148(13):134116. doi: 10.1063/1.5024869.
We present significant algorithmic improvements to a recently proposed direct quantum dynamics method, based upon combining well established grid-based quantum dynamics approaches and expansions of the potential energy operator in terms of a weighted sum of Gaussian functions. Specifically, using a sum of low-dimensional Gaussian functions to represent the potential energy surface (PES), combined with a secondary fitting of the PES using singular value decomposition, we show how standard grid-based quantum dynamics methods can be dramatically accelerated without loss of accuracy. This is demonstrated by on-the-fly simulations (using both standard grid-based methods and multi-configuration time-dependent Hartree) of both proton transfer on the electronic ground state of salicylaldimine and the non-adiabatic dynamics of pyrazine.
我们对最近提出的一种直接量子动力学方法进行了重大的算法改进，该方法基于结合了成熟的基于网格的量子动力学方法和用加权高斯函数和表示的势能算子展开。具体来说，使用低维高斯函数的和来表示势能面（PES），并结合奇异值分解对 PES 进行二次拟合，我们展示了如何在不损失准确性的情况下，大大加速标准基于网格的量子动力学方法。这通过对水杨醛亚胺电子基态上的质子转移和吡嗪的非绝热动力学的实时模拟（同时使用标准基于网格的方法和多组态含时哈特ree）得到了证明。
