Department of Chemistry, University of California, Berkeley, California 94720, USA.
J Chem Phys. 2013 Nov 14;139(18):181101. doi: 10.1063/1.4829536.
We present a Jastrow-factor-inspired variant of coupled cluster theory that accurately describes both weak and strong electron correlation. Compatibility with quantum Monte Carlo allows for variational energy evaluations and an antisymmetric geminal power reference, two features not present in traditional coupled cluster that facilitate a nearly exact description of the strong electron correlations in minimal-basis N2 bond breaking. In double-ζ treatments of the HF and H2O bond dissociations, where both weak and strong correlations are important, this polynomial cost method proves more accurate than either traditional coupled cluster or complete active space perturbation theory. These preliminary successes suggest a deep connection between the ways in which cluster operators and Jastrow factors encode correlation.
我们提出了一种受 Jastrow 因子启发的耦合簇理论变体，该变体可以准确描述弱和强电子相关。与量子蒙特卡罗的兼容性允许变分能量评估和反对称双子幂参考，这两个在传统耦合簇中不存在的特性，有助于在最小基 N2 键断裂中对强电子相关进行几乎完全的描述。在 HF 和 H2O 键离解的双 ζ 处理中，弱相关和强相关都很重要，这种多项式成本方法证明比传统的耦合簇或完全活性空间微扰理论更准确。这些初步的成功表明，簇算子和 Jastrow 因子编码相关的方式之间存在着深刻的联系。
