Single‐reference coupled cluster methods for computing excitation energies in large molecules: The efficiency and accuracy of approximations

Abstract

AbstractWhile methodological developments in the last decade made it possible to compute coupled cluster (CC) energies including excitations up to a perturbative triples correction for molecules containing several hundred atoms, a similar breakthrough has not yet been reported for excited state computations. Accurate CC methods for excited states are still expensive, although some promising candidates for an efficient and accurate excited state CC method have emerged recently. This review examines the various approximation schemes with particular emphasis on their performance for excitation energies and summarizes the best state‐of‐the‐art results which may pave the way for a robust excited state method applicable to molecules of hundreds of atoms. Among these, special attention will be given to exploiting the techniques of similarity transformation, perturbative approximations as well as integral decomposition, local and embedding techniques within the equation of motion CC framework.This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Structure and Mechanism > Molecular Structures