Nonorthogonal Active Space Decomposition of Wave Functions with Multiple Correlation Mechanisms
Nonorthogonal Active Space Decomposition of Wave Functions with Multiple Correlation Mechanisms
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DOI：
10.1021/acs.jpclett.2c03349
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发表时间：
2022-12-21
影响因子：
5.7
通讯作者：
Thompson, Lee M.
中科院分区：
文献类型：
--
作者：
Kempfer-Robertson, Emily M.;Mahler, Andrew D.;Thompson, Lee M.
提出非正交活动空间分解（NO-ASD）方法来描述包含多个相关机制的系统。 NO-ASD通过相关机制划分波函数，使得不同相关机制之间的相互作用用有效的哈密顿方法处理，而同一相关机制中的相关轨道之间的相互作用被明确地处理。因此，行列式展开与相关机制的数量呈多项式缩放，而不是呈指数缩放，这显着减少了与相关轨道空间大小相关的阶乘缩放。尽管 NO-ASD 具有非正交框架，但该方法在执行正交行列式展开的非正交耦合时可以利用计算高效的矩阵元素评估。在这项工作中，我们介绍并检查了 NOASD 方法与完整的主动空间方法的比较，以确定 NO-ASD 方法如何降低问题维度及其影响相关能量恢复量的程度。对臭氧、镍乙炔和 mu-氧二铜氨异构体进行了计算。
The nonorthogonal active space decomposition (NO-ASD) methodology is proposed for describing systems containing multiple correlation mechanisms. NO-ASD partitions the wave function by a correlation mechanism, such that the interactions between different correlation mechanisms are treated with an effective Hamiltonian approach, while interactions between correlated orbitals in the same correlation mechanism are treated explicitly. As a result, the determinant expansion scales polynomially with the number of correlation mechanisms rather than exponentially, which significantly reduces the factorial scaling associated with the size of the correlated orbital space. Despite the nonorthogonal framework of NO-ASD, the approach can take advantage of computational efficient matrix element evaluation when performing nonorthogonal coupling of orthogonal determinant expansions. In this work, we introduce and examine the NOASD approach in comparison to complete active space methods to establish how the NO-ASD approach reduces the problem dimensionality and the extent to which it affects the amount of correlation energy recovered. Calculations are performed on ozone, nickel-acetylene, and isomers of mu-oxo dicopper ammonia.