The enthalpies of formation of AsXnmolecules, where X = H, F or Cl, and n = 1, 2 or 3, by RCCSD(T) and UCCSD(T)-F12x calculations

Kam Wah Mok, Edmond P.F. Lee, Foo Tim Chau, John M. Dyke

Research output: Journal article publicationJournal articleAcademic researchpeer-review

15 Citations (Scopus)

Abstract

RCCSD(T) and UCCSD(T)-F12x calculations were performed on AsXnmolecules, where X = H, F or Cl, and n = 1, 2 or 3, and related species, in order to evaluate their enthalpies of formation (ΔHfØ). The recommended ΔHfØvalues obtained from the present investigation are AsH, 57.7(2); AsF, -7.9(3); AsCl, 27.2(4); AsH2, 39.8(4); AsF2, -96.6(9); AsCl2, -17.8(10); AsH3, 17.1(4); AsF3-196.0(5) and AsCl3, -59.1(27) kcal mole-1. These values are anchored only on one thermodynamic quantity, namely, ΔHfØ(As) (= 70.3 kcal mole-1). In the calculations, the fully-relativistic small-core effective core potential (ECP10MDF) was used for As. Contributions from outer core correlation of As 3d10electrons were computed explicitly in both RCCSD(T) and UCCSD(T)-F12 calculations with additional tight basis functions designed for As 3d10electrons. Basis sets of up to augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality were used in RCCSD(T) calculations and computed relative electronic energies were extrapolated to the complete basis set (CBS) limit. For the simplified, explicitly correlated UCCSD(T)-F12x calculations, basis sets of up to quadruple-zeta (QZ) quality were employed. Based on the RCCSD(T)/CBS benchmark values, the reliability of available theoretical and experimental values have been assessed.
Original languageEnglish
Pages (from-to)9540-9553
Number of pages14
JournalPhysical Chemistry Chemical Physics
Volume13
Issue number20
DOIs
Publication statusPublished - 28 May 2011

ASJC Scopus subject areas

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

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