Rank-reduced equation-of-motion coupled cluster triples: an accurate and affordable way of calculating electronic excitation energies

TL;DR

The paper introduces RR-EOM-CC3, a tensor-decomposition-based method that reduces computational cost and maintains high accuracy in calculating electronic excitation energies for large molecules.

Contribution

It presents a novel rank-reduction approach for EOM-CC3 using Tucker-3 tensor decomposition, enabling scalable and accurate excitation energy calculations.

Findings

Achieves errors smaller than canonical EOM-CC3 compared to FCI.

Reduces computational scaling to N^6, enabling larger system calculations.

Demonstrates efficiency on large molecules like L-proline and heptazine.

Abstract

In the present work we report an implementation of the rank-reduced equation-of-motion coupled cluster method with approximate triple excitations (RR-EOM-CC3). The proposed variant relies on tensor decomposition techniques in order to alleviate the high cost of computing and manipulating the triply-excited amplitudes. In the RR-EOM-CC3 method, both ground-state and excited-state triple-excitation amplitudes are compressed according to the Tucker-3 format. This enables to factorize the working equations such that the formal scaling of the method is reduced to $N^6$, where $N$ is the system size. An additional advantage of our method is the fact the accuracy can be strictly controlled by proper choice of two parameters defining sizes of triple-excitation subspaces in the Tucker decomposition for the ground and excited states. Optimal strategies of selecting these parameters are discussed. The developed method has been tested in a series of calculations of electronic excitation energies and compared to its canonical EOM-CC3 counterpart. Errors several times smaller than the inherent error of the canonical EOM-CC3 method (in comparison to FCI) are straightforward to achieve. This conclusion holds both for valence states dominated by single excitations and for states with pronounced doubly-excited character. Taking advantage of the decreased scaling, we demonstrate substantial computational costs reductions (in comparison with the canonical EOM-CC3) in the case of two large molecules -- L-proline and heptazine. This illustrates the usefulness of the RR-EOM-CC3 method for accurate determination of excitation energies of large molecules.