Linear-response density cumulant theory for excited electronic states

TL;DR

This paper introduces a linear-response formulation of density cumulant theory (DCT) for excited states, demonstrating improved accuracy over traditional methods like EOM-CCSD in small molecules and complex excited states.

Contribution

The paper develops and implements linear-response DCT (LR-ODC-12), providing a balanced and accurate method for excited state calculations, outperforming some existing approaches.

Findings

LR-ODC-12 shows smaller mean absolute errors than EOM-CCSD for excitation energies.

LR-ODC-12 accurately describes relative energies of complex excited states.

Results demonstrate LR-ODC-12 as a promising approach for excited state studies.

Abstract

We present a linear-response formulation of density cumulant theory (DCT) that provides a balanced and accurate description of many electronic states simultaneously. In the original DCT formulation, only information about a single electronic state (usually, the ground state) is obtained. We discuss the derivation of linear-response DCT, present its implementation for the ODC-12 method (LR-ODC-12), and benchmark its performance for excitation energies in small molecules (N$_2$, CO, HCN, HNC, C$_2$H$_2$, and H$_2$CO), as well as challenging excited states in ethylene, butadiene, and hexatriene. For small molecules, LR-ODC-12 shows smaller mean absolute errors in excitation energies than equation-of-motion coupled cluster theory with single and double excitations (EOM-CCSD), relative to the reference data from EOM-CCSDT. In a study of butadiene and hexatriene, LR-ODC-12 correctly describes the relative energies of the singly-excited $1^1\mathrm{B_{u}}$ and the doubly-excited $2^1\mathrm{A_{g}}$ states, in excellent agreement with highly accurate semistochastic heat-bath configuration interaction results, while EOM-CCSD overestimates the energy of the $2^1\mathrm{A_{g}}$ state by almost 1 eV. Our results demonstrate that linear-response DCT is a promising theoretical approach for excited states of molecules.