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Title: Benchmarking the completely renormalised equation-of-motion coupled-cluster approaches for vertical excitation energies

When vertical energies are excited for a comprehensive test set of about 150 singlet excited states of 28 medium-sized organic molecules computed using two variants of the completely renormalised (CR) equation-of-motion (EOM) coupled-cluster (CC) method with singles, doubles, and non-iterative triples, abbreviated as δ-CR-EOMCCSD(T), and the analogous two variants of the newer, left-eigenstate δ-CR-EOMCC(2,3) approach are benchmarked against the previously published CASPT2, CC3, and EOMCCSDT-3 results, as well as the suggested theoretical best estimate (TBE) values. The δ-CR-EOMCC approaches are also used to identify and characterise about 50 additional excited states, including several states having substantial two-electron excitation components, which have not been found in the previous work and which can be used in future benchmark studies. We demonstrated that the non-iterative triples corrections to the EOMCCSD excitation energies defining the relatively inexpensive, single-reference, black-box δ-CR-EOMCC approaches provide significant improvements in the EOMCCSD data, while closely matching the results of the iterative and considerably more expensive CC3 and EOMCCSDT-3 calculations and their CASPT2 and TBE counterparts. It is also shown that the δ-CR-EOMCC methods, especially δ-CR-EOMCC(2,3), are capable of bringing the results of the CC3 and EOMCCSDT-3 calculations to a closer agreement with the CASPT2 and TBE data, demonstrating themore » utility of the cost-effective δ-CR-EOMCC methods in applications involving molecular electronic spectra. Finally, we show that there may exist a relationship between the magnitude of the triples corrections defining δ-CR-EOMCC approaches and the reduced excitation level diagnostic resulting from EOMCCSD.« less
 [1] ;  [1] ;  [1]
  1. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Molecular Physics
Additional Journal Information:
Journal Volume: 113; Journal Issue: 19-20; Journal ID: ISSN 0026-8976
Taylor & Francis
Research Org:
Michigan State Univ., East Lansing, MI (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; equation-of-motion coupled-cluster methods; completely renormalized approaches; non-iterative triples corrections; electronically excited states; benchmarking quantum chemistry methods
OSTI Identifier: