Accuracy of coupled cluster excitation energies in diffuse basis sets

Dániel Kánnár, A. Tajti, Péter G. Szalay

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

We present a comprehensive statistical analysis on the accuracy of various excited state Coupled Cluster methods, accentuating the effect of diffuse basis sets on vertical excitation energies of valence and Rydberg-type states. Many popular approximate doubles and triples methods are benchmarked with basis sets up to aug-cc-pVTZ, with high level EOMCCSDT results used as reference. The results reveal a serious deficiency of CC2 linear response and CIS(D) techniques in the description of Rydberg states, a feature not shown by the EOM-CCSD(2) and EOM-CCSD variants. The CC3 theory proves to be an accurate choice among the iterative approximate triples methods, while the novel perturbation-based CCSD(T)(a) variant turns out to be the best way to include the effect of triple excitations in a noniterative way.

Original languageEnglish
Pages (from-to)202-209
Number of pages8
JournalJournal of Chemical Theory and Computation
Volume13
Issue number1
DOIs
Publication statusPublished - Jan 1 2017

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Rydberg states
Excitation energy
Excited states
Statistical methods
excitation
Commonwealth of Independent States
statistical analysis
energy
valence
perturbation

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

Accuracy of coupled cluster excitation energies in diffuse basis sets. / Kánnár, Dániel; Tajti, A.; Szalay, Péter G.

In: Journal of Chemical Theory and Computation, Vol. 13, No. 1, 01.01.2017, p. 202-209.

Research output: Contribution to journalArticle

Kánnár, Dániel ; Tajti, A. ; Szalay, Péter G. / Accuracy of coupled cluster excitation energies in diffuse basis sets. In: Journal of Chemical Theory and Computation. 2017 ; Vol. 13, No. 1. pp. 202-209.
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