McCormack Drew A
Theoretische Chemie, Faculteit Exacte Wetenschappen, Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
J Chem Phys. 2006 May 28;124(20):204101. doi: 10.1063/1.2196889.
We investigate the viability of dynamical pruning of localized basis sets in time-dependent quantum wave packet methods. Basis functions that have a very small population at any given time are removed from the active set. The basis functions themselves are time independent, but the set of active functions changes in time. Two different types of localized basis functions are tested: discrete variable representation (DVR) functions, which are localized in position space, and phase-space localized (PSL) functions, which are localized in both position and momentum. The number of functions active at each point in time can be as much as an order of magnitude less for dynamical pruning than for static pruning, in reactive scattering calculations of H2 on the Pt(211) stepped surface. Scaling of the dynamically pruned PSL (DP-PSL) bases with dimension is considerably more favorable than for either the primitive (direct product) or DVR bases, and the DP-PSL basis set is predicted to be three orders of magnitude smaller than the primitive basis set in the current state-of-the-art six-dimensional reactive scattering calculations.
我们研究了在含时量子波包方法中对定域基组进行动态删减的可行性。在任何给定时刻占据数非常小的基函数会从活动集中移除。基函数本身与时间无关，但活动函数集随时间变化。我们测试了两种不同类型的定域基函数：在位置空间定域的离散变量表示（DVR）函数，以及在位置和动量上都定域的相空间定域（PSL）函数。在Pt(211)阶梯表面上H₂的反应性散射计算中，对于动态删减，每个时刻的活动函数数量比静态删减时少一个数量级之多。动态删减的PSL（DP - PSL）基组随维度的缩放比原始（直积）基组或DVR基组都更有利，并且在当前最先进的六维反应性散射计算中，DP - PSL基组预计比原始基组小三个数量级。
