Tensor Hypercontraction Form of the Perturbative Triples Energy in Coupled-Cluster Theory

Fuente: arXiv
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Main Authors: Jiang, Andy, Turney, Justin M., Schaefer III, Henry F.
Format: Preprint
Published: 2022
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author Jiang, Andy
Turney, Justin M.
Schaefer III, Henry F.
author_facet Jiang, Andy
Turney, Justin M.
Schaefer III, Henry F.
contents We present the working equations for a reduced-scaling method of evaluating the perturbative triples (T) energy in coupled-cluster theory, through the tensor hypercontraction (THC) of the triples amplitudes ($t_{ijk}^{abc}$). Through our method we can reduce the scaling of the (T) energy from the traditional O($N^{7}$) to a more modest O($N^{5}$). We also discuss implementation details to aid future research, development, and software realization of this method. Additionally, we show that this method yields sub-millihartree (mEh) differences from CCSD(T) when evaluating absolute energies, and sub-0.1 kcal/mol energy differences when evaluating relative energies. Finally, we demonstrate that this method converges to the true CCSD(T) energy through the systematic increasing of the rank or eigenvalue tolerance of the orthogonal projector, as well as exhibiting sub-linear to linear error growth with respect to system size.
format Preprint
id arxiv_https___arxiv_org_abs_2210_07035
institution arXiv
publishDate 2022
record_format arxiv
spellingShingle Tensor Hypercontraction Form of the Perturbative Triples Energy in Coupled-Cluster Theory
Jiang, Andy
Turney, Justin M.
Schaefer III, Henry F.
Chemical Physics
We present the working equations for a reduced-scaling method of evaluating the perturbative triples (T) energy in coupled-cluster theory, through the tensor hypercontraction (THC) of the triples amplitudes ($t_{ijk}^{abc}$). Through our method we can reduce the scaling of the (T) energy from the traditional O($N^{7}$) to a more modest O($N^{5}$). We also discuss implementation details to aid future research, development, and software realization of this method. Additionally, we show that this method yields sub-millihartree (mEh) differences from CCSD(T) when evaluating absolute energies, and sub-0.1 kcal/mol energy differences when evaluating relative energies. Finally, we demonstrate that this method converges to the true CCSD(T) energy through the systematic increasing of the rank or eigenvalue tolerance of the orthogonal projector, as well as exhibiting sub-linear to linear error growth with respect to system size.
title Tensor Hypercontraction Form of the Perturbative Triples Energy in Coupled-Cluster Theory
topic Chemical Physics
url https://arxiv.org/abs/2210.07035