Robust Tensor Hypercontraction of the Particle-Particle Ladder Term in Equation-of-Motion Coupled Cluster Theory

TL;DR

This paper introduces a robust least-squares tensor hypercontraction method for the particle-particle ladder term in equation-of-motion coupled cluster theory, significantly reducing computational cost while maintaining high accuracy.

Contribution

It implements the R-LS-THC approach for EOM-CC methods, enabling efficient and accurate calculations of excitation and electron attachment energies.

Findings

Errors around 1 meV achieved

Calculation time reduced by approximately 5 times

High accuracy maintained in benchmark tests

Abstract

One method of representing a high-rank tensor as a (hyper-)product of lower-rank tensors is the tensor hypercontraction (THC) method of Hohenstein et al. This strategy has been found to be useful for reducing the polynomial scaling of coupled-cluster methods by representation of a four dimensional tensor of electron-repulsion integrals in terms of five two-dimensional matrices. Pierce et al. have already shown that the application of a robust form of THC to the particle-particle ladder term (PPL) reduces the cost of this term in couple-cluster singles and doubles (CCSD) from $\mathcal{O} (N^6)$ to $\mathcal{O} (N^5)$ with negligible errors in energy with respect to the density-fitted variant. In this work we have implemented the least-squares variant of THC (LS-THC) which does not require a non-linear tensor factorization, including the robust form (R-LS-THC), for the calculation of the excitation and electron attachment energies using equation-of-motion coupled cluster methods EOMEE-CCSD and EOMEA-CCSD, respectively. We have benchmarked the effect of the R-LS-THC-PPL approximation on excitation energies using the comprehensive QUEST database and the accuracy of electron attachment energies using the NAB22 database. We find that errors on the order of 1 meV are achievable with a reduction in total calculation time of approximately $5\times$.