The barrier to linearity of water

György Tarczay, Attila G. Császár, Wim Klopper, Viktor Szalay, Wesley D. Allen, Henry F. Schaefer

Research output: Contribution to journalArticle

64 Citations (Scopus)


High-quality ab initio quantum chemical methods, including higher-order coupled cluster (CC) and many-body perturbation (MP) theory, explicitly correlated (linear R12) techniques, and full configuration interaction (FCI) benchmarks, with basis sets ranging from [O/H] [3s2p1d/2s1p] to [8s7p6d5f4g3h2i/7s6p5d4f3g2h] have been employed to obtain the best possible value for the barrier to linearity of water. Attention is given to the degree of accord among extrapolations of conventional MP2, CCSD, and CCSD(T) energies to the complete basis set (CBS) limit and corresponding linear R12 schemes for these correlation methods. Small corrections due to one- and two-particle relativistic terms, core correlation effects, and the diagonal Born-Oppenheimer correction (DBOC) have been incorporated. The final electronic (vibrationless) extrapolated barrier height of this study is 11 127 ± 35 cm-1. Anharmonic force fields have been determined at the aug-cc-pCVTZ CCSD(T) level at equilibrium and at a linear reference geometry. These and previous sextic force fields are in general accord with the expansion terms of recent global potential energy hypersurfaces but also highlight some of their weaknesses.

Original languageEnglish
Pages (from-to)11971-11981
Number of pages11
JournalJournal of Chemical Physics
Issue number24
Publication statusPublished - Jun 22 1999

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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