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

Mok, Daniel K.W., Lee, Edmond P.F., Chau, Foo-tim and Dyke, John M. (2011) The enthalpies of formation of AsXn molecules, where X= H, F, or Cl, and n=1,2 or 3 by RCCSD(T) and UCCSD(T)-F12x calculations. Physical Chemistry Chemical Physics, 13 (20), 9540-9553. (doi:10.1039/C1CP20490D).

Abstract

RCCSD(T) and UCCSD(T)-F12x calculations were performed on AsXn molecules, where X = H, F or Cl, and n = 1, 2 or 3, and related species, in order to evaluate their enthalpies of formation (?HfØ). The recommended ?HfØ values 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, ?HfØ(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 3d10 electrons were computed explicitly in both RCCSD(T) and UCCSD(T)-F12 calculations with additional tight basis functions designed for As 3d10 electrons. 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.

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Contributors

Author: John M. Dyke

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