A Cholesky decomposition-based implementation of relativistic two-component coupled-cluster methods for medium-sized molecules

TL;DR

This paper introduces a Cholesky decomposition-based implementation of relativistic two-component coupled-cluster methods, enabling efficient and accurate calculations for medium-sized molecules, including uranium compounds, with reduced computational cost.

Contribution

It presents a novel CD-based implementation of X2CAMF-CC and EOM-CC methods that extends applicability to larger molecules by avoiding complex integral constructions.

Findings

Cholesky threshold of 10^{-4} maintains chemical accuracy.

Successfully computed bond-dissociation energy of UF₆ with quadruple-zeta basis.

Accurately determined excitation energy of solvated uranyl ion.

Abstract

A Cholesky decomposition (CD)-based implementation of relativistic two-component coupled-cluster (CC) and equation-of-motion CC (EOM-CC) methods using an exact two-component Hamiltonian augmented with atomic-mean-field spin-orbit integrals (the X2CAMF scheme) is reported. The present CD-based implementation of X2CAMF-CC and EOM-CC methods employs atomic-orbital-based algorithms to avoid the construction of two-electron integrals and intermediates involving three and four virtual indices. Our CD-based implementation extends the applicability of X2CAMF-CC and EOM-CC methods to medium-sized molecules with the possibility to correlate around 1000 spinors. Benchmark calculations for uranium-containing small molecules have been performed to assess the dependence of the CC results on the Cholesky threshold. A Cholesky threshold of $10^{-4}$ is shown to be sufficient to maintain chemical accuracy. Example calculations to illustrate the capability of the CD-based relativistic CC methods are reported for the bond-dissociation energy of the uranium hexafluoride molecule, UF$_6$, with up to quadruple-zeta basis sets, and the lowest excitation energy in solvated uranyl ion [UO$_2^{2+}$(H$_2$O)$_{12}$].