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首页> 外文期刊>The Journal of Chemical Physics >Variational optimization of the two-electron reduced-density matrix under pure-state N-representability conditions
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Variational optimization of the two-electron reduced-density matrix under pure-state N-representability conditions

机译：纯态N可表示性条件下双电子密度矩阵的变分优化

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摘要

The direct variational optimization of the ground-state two-electron reduced-density matrix (2-RDM) is typically performed under ensemble N-representability conditions. Accordingly, variationally obtained 2-RDMs for degenerate ground states may not represent a pure state. When considering only ground-state energetics, the ensemble nature of the 2-RDM is of little consequence. However, the use of ensemble densities within an extended random phase approximation (ERPA) yields astonishingly poor estimates of excitation energies, even for simple atomic systems [H. van Aggelen et al., Comput. Theor. Chem. 1003, 50-54 (2013)]. Here, we outline an approach for the direct variational optimization of ground-state 2-RDMs that satisfy pure-state N-representability known as generalized Pauli constraints. Within the ERPA, 2-RDMs that satisfy both ensemble conditions and the generalized Pauli constraints yield much more reliable estimates of excitation energies than those that satisfy only ensemble conditions. Published by AIP Publishing.
机译：基态双电子降低密度矩阵（2-RDM）的直接变分优化通常在整体N可表示性条件下执行。因此，用于简并基态的差异获得的2-RDM可能不代表纯态。仅考虑基态能量学时，2-RDM的整体性质几乎没有影响。然而，即使对于简单的原子系统，在扩展的随机相位近似（ERPA）中使用集合密度也会产生令人震惊的不良激发能估计值[H. van Aggelen等人，计算机。理论。化学1003，50-54（2013）]。在这里，我们概述了一种满足基态2-RDM的直接变分优化的方法，该方法可以满足被称为广义Pauli约束的纯态N可表示性。在ERPA中，同时满足集合条件和广义Pauli约束的2-RDM产生的激发能估计要比仅满足集合条件的激发能可靠得多。由AIP Publishing发布。

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