<i>Dark</i> Doubly Excited States with Modified Coupled Cluster Models: A Reliable Compromise between Cost and Accuracy?
Varun Rishi, Moneesha Ravi, Ajith Perera, Rodney J. Bartlett
Abstract
To treat doubly excited states, the treatment of triple excitations is considered necessary in the framework of equation-of-motion coupled cluster (EOM-CC) methods. We investigate models without explicit triples and seek quantitative measure for the performance of EOM based on CC with singles and doubles (CCSD) or modified CCSD (Distinguishable Cluster Approximation) approaches for states with predominant double excitation character. We also test the efficacy of including triples in perturbative manner through EOM-CCSD(T) and in an iterative way through EOM-CCSDT-3 method. Extended similarity transformed EOM-CCSD(EXT-STEOM-CCSD) method is also tested and provides superior quality results at comparatively low cost. We use the QUEST2 benchmark set of double excitations proposed by Loos et al. [ J. Chem. Theory Comput. 2019, 15, 1939] to investigate the performance of methods such as EOM-CCSD, EOM-DCSD, EXT-STEOM-CCSD, ΔCCSD, and ΔDCSD. We also test a tailored CC approach, ΔpairCCD-TCCSD.