Exploration of Reduced Scaling Formulation of Equation of Motion Coupled-Cluster Singles and Doubles Based on State-Averaged Pair Natural Orbitals

TL;DR

This paper introduces a reduced-complexity, state-averaged PNO-based EOM-CCSD method for excited states, demonstrating improved robustness and efficiency for large molecular systems with accurate excitation energies.

Contribution

The paper develops a novel state-averaged PNO-EOM-CCSD approach that enhances robustness and efficiency for excited state calculations in large systems.

Findings

Errors in excitation energies are below 0.02 eV for tested molecules.

The approach is robust against root flipping and degeneracies.

It is more economical for large manifolds of states.

Abstract

A reduced-complexity variant of equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) method is formulated in terms of state-averaged excited state pair natural orbitals (PNO) designed to describe manifolds of excited states. State-averaged excited state PNOs for the {\em target} manifold are determined by averaging CIS(D) pair densities over the computational manifold. To assess the performance of PNO-EOM-CCSD approach on extended systems the new massively parallel canonical EOM-CCSD program has been developed in the Massively Parallel Quantum Chemistry program that allows treatment of systems with 50+ atoms using realistic basis sets with 1000+ functions. The use of state-averaged PNOs offers several potential advantages relative to the recently proposed state-specific PNOs: our approach is robust with respect to root flipping and state degeneracies, it is more economical when computing large manifolds of states, and it simplifies evaluation of transition-specific observables such as dipole moments. With the PNO truncation threshold of $10^{-7}$, the errors in excitation energies are on average below 0.02 eV for the first six singlet states of 28 organic molecules included in the standard test set of Thiel and co-workers (J. Chem. Phys. 2008, 128, 134110) with 50-70 state-averaged PNOs per pair.