Equilibrium inversion barrier of NH3 from extrapolated coupled-cluster pair energies

Wim Klopper, Claire C M Samson, G. Tarczay, A. Császár

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

The basis-set convergence of singlet and triplet pair energies of coupled-cluster theory including single and double excitations is accelerated by means of extrapolations based on the distinct convergence behaviors of these pairs. The new extrapolation procedure predicts an nonrelativistic Born-Oppenheimer inversion barrier of 1767 ± 12 cm-1 for NH3. An effective one-dimensional, vibrationally averaged barrier of 2021 ± 20 cm-1 is obtained when relativistic effects (+20 cm-1), Born-Oppenheimer diagonal corrections (-10 cm-1), and zero-point vibrations (+244 cm-1) are accounted for.

Original languageEnglish
Pages (from-to)1306-1314
Number of pages9
JournalJournal of Computational Chemistry
Volume22
Issue number13
DOIs
Publication statusPublished - Oct 2001

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Extrapolation
Inversion
Set Convergence
Zero Point
Energy
Vibration
Excitation
Distinct
Predict

Keywords

  • Ammonia
  • Basis-set convergence
  • Coupled-cluster theory
  • Inversion barrier
  • Pair energies

ASJC Scopus subject areas

  • Chemistry(all)
  • Safety, Risk, Reliability and Quality

Cite this

Equilibrium inversion barrier of NH3 from extrapolated coupled-cluster pair energies. / Klopper, Wim; Samson, Claire C M; Tarczay, G.; Császár, A.

In: Journal of Computational Chemistry, Vol. 22, No. 13, 10.2001, p. 1306-1314.

Research output: Contribution to journalArticle

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AB - The basis-set convergence of singlet and triplet pair energies of coupled-cluster theory including single and double excitations is accelerated by means of extrapolations based on the distinct convergence behaviors of these pairs. The new extrapolation procedure predicts an nonrelativistic Born-Oppenheimer inversion barrier of 1767 ± 12 cm-1 for NH3. An effective one-dimensional, vibrationally averaged barrier of 2021 ± 20 cm-1 is obtained when relativistic effects (+20 cm-1), Born-Oppenheimer diagonal corrections (-10 cm-1), and zero-point vibrations (+244 cm-1) are accounted for.

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