Equation-of-motion/Linear-response Coupled Cluster Methods with an Approximate Treatment on Triples for Singly-excited States with Pronounced Double Excitation Character

doi:10.1007/s40242-023-3035-z

Abstract

Abstract: In this work, we investigate the performance of various equation- of-motion/linear-response coupled cluster (EOM/LR-CC) methods with an approximate treatment for triples on excitation energies (EEs) by comparing with EOM-CCSDT (SDT=single, double, triple excitations) results. The focus of this work is on singly-excited states with percentages of the single excitation part (R₁, %) from CC3 between 50% and 80%, i.e., excited states with a pronounced double excitation character. CC3 is shown to provide EEs that agree well with EOM-CCSDT results for such excited states. Moreover, reliable EEs can be obtained with EOM-CCSD (T) (a)^* and CCSDR (3) for excited states with R₁ from CC3 larger than 80%. As for singly-excited states with R₁ from CC3 between 80% and 50%, EEs with EOM-CCSD^*, CCSDR (T) and δ-CR-EOM-CC (2,3)-D agree reasonably well with those of EOM-CCSDT. However, it is too costly to choose a proper method for singly-excited states based on R₁ of CC3 since CC3 is a rather expensive method. On the other hand, our results show that difference between EEs with EOM-CCSD and EOM-CCSD (T) (a)^* [ΔE_{(T) (a)^*}] correlates well with R₁ from CC3 and ΔE_{(T) (a)^*} is about 0.25 eV when R₁ (CC3) is 80%. Appropriate methods to obtain reasonable EEs for singly-excited state can be chosen based on whether ΔE_{(T) (a)^*} is larger than 0.25 eV

Key words: Excitation energy, Equation-of-motion/linear-response coupled cluster theory, Double excitation character, Triple excitation

HU Yanmei, LU Yanzhao, WANG Zhifan, and WANG Fan. Equation-of-motion/Linear-response Coupled Cluster Methods with an Approximate Treatment on Triples for Singly-excited States with Pronounced Double Excitation Character[J]. Chemical Research in Chinese Universities, 2023, 39(6): 998-1004.

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