Spatial Signatures of Electron Correlation in Least-Squares Tensor Hypercontraction.

IF 2.7 2区 化学 Q3 CHEMISTRY, PHYSICAL
The Journal of Physical Chemistry A Pub Date : 2025-01-23 Epub Date: 2025-01-09 DOI:10.1021/acs.jpca.4c06666
Chao Yin, Sara Beth Becker, James H Thorpe, Devin A Matthews
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引用次数: 0

Abstract

Least-squares tensor hypercontraction (LS-THC) has received some attention in recent years as an approach to reduce the significant computational costs of wave function-based methods in quantum chemistry. However, previous work has demonstrated that LS-THC factorization performs disproportionately worse in the description of wave function components (e.g., cluster amplitudes 2) than Hamiltonian components (e.g., electron repulsion integrals (pq|rs)). This work develops novel theoretical methods to study the source of these errors in the context of the real-space 2 kernel, and reports, for the first time, the existence of a "correlation feature" in the errors of the LS-THC representation of the "exchange-like" correlation energy EX and 2 that is remarkably consistent across ten molecular species, three correlated wave functions, and four basis sets. This correlation feature portends the existence of a "pair point kernel" missing in the usual LS-THC representation of the wave function, which critically depends upon pairs of grid points situated close to atoms and with interpair distances between one and two Bohr radii. These findings point the way for future LS-THC developments to address these shortcomings.

最小二乘张量超缩中电子相关的空间特征。
近年来,最小二乘张量超收缩(LS-THC)作为一种减少量子化学中基于波函数方法的大量计算成本的方法受到了一些关注。然而,先前的工作已经证明,LS-THC分解在波函数分量(例如簇振幅T³)的描述方面比哈密顿分量(例如电子排斥积分(pq|rs))表现得更差。本研究开发了新的理论方法,在实空间T²核的背景下研究这些误差的来源,并首次报道了在“类交换”相关能EX和T²的LS-THC表示的误差中存在“相关特征”,该特征在10个分子种、3个相关波函数和4个基集之间显着一致。这种相关特征预示着在通常的LS-THC波函数表示中缺失的“对点核”的存在,这主要取决于位于原子附近的网格点对,并且对间距离在一到两个玻尔半径之间。这些发现为未来LS-THC的发展指明了解决这些缺点的方向。
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来源期刊
The Journal of Physical Chemistry A
The Journal of Physical Chemistry A 化学-物理:原子、分子和化学物理
CiteScore
5.20
自引率
10.30%
发文量
922
审稿时长
1.3 months
期刊介绍: The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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