Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
J Chem Phys. 2010 Jan 28;132(4):041103. doi: 10.1063/1.3302277.
We provide a very simple adaptation of our recently published quantum Monte Carlo algorithm in full configuration-interaction (Slater determinant) spaces which dramatically reduces the number of walkers required to achieve convergence. A survival criterion is imposed for newly spawned walkers. We define a set of initiator determinants such that progeny of walkers spawned from such determinants onto unoccupied determinants are able to survive, while the progeny of walkers not in this set can survive only if they are spawned onto determinants which are already occupied. The set of initiators is originally defined to be all determinants constructable from a subset of orbitals, in analogy with complete-active spaces. This set is dynamically updated so that if a noninitiator determinant reaches an occupation larger than a preset limit, it becomes an initiator. The new algorithm allows sign-coherent sampling of the FCI space to be achieved with relatively few walkers. Using the N(2) molecule as an illustration, we show that rather small initiator spaces and numbers of walkers can converge with submilliHartree accuracy to the known full configuration-interaction (FCI) energy (in the cc-pVDZ basis), in both the equilibrium geometry and the multiconfigurational stretched case. We use the same method to compute the energy with cc-pVTZ and cc-pVQZ basis sets, the latter having an FCI space of over 10(15) with very modest computational resources.
我们提供了一种非常简单的自适应方法,用于在全组态相互作用(Slater 行列式)空间中应用我们最近发表的量子蒙特卡罗算法,该方法极大地减少了实现收敛所需的walker 数量。我们对新生成的walker 施加了生存准则。我们定义了一组起始行列式,使得从这些行列式上产生的walker 的后代能够在未占据的行列式上生存,而不在这个集合中的walker 的后代只有在它们被产生到已经被占据的行列式上时才能生存。起始集最初定义为可以从一组轨道构造的所有行列式,类似于完全活性空间。这个集合是动态更新的,因此如果一个非起始行列式达到超过预设限制的占据数,它就会成为一个起始行列式。新算法允许用相对较少的walker 实现 FCI 空间的符号相干采样。我们以 N(2)分子为例,展示了在平衡几何形状和多组态拉伸情况下,使用较小的起始空间和 walker 数量,就可以用 submilliHartree 的精度收敛到已知的全组态相互作用(FCI)能量(在 cc-pVDZ 基中)。我们使用相同的方法计算 cc-pVTZ 和 cc-pVQZ 基组的能量,后者的 FCI 空间超过 10(15),但计算资源非常有限。