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The enthalpies of formation of AsX(n) molecules, where X = H, F or Cl, and n = 1, 2 or 3, by RCCSD(T) and UCCSD(T)-F12x calculations.
MedLine Citation:
PMID:  21487636     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
RCCSD(T) and UCCSD(T)-F12x calculations were performed on AsX(n) molecules, where X = H, F or Cl, and n = 1, 2 or 3, and related species, in order to evaluate their enthalpies of formation (ΔH(f)(Ø)). The recommended ΔH(f)(Ø) values obtained from the present investigation are AsH, 57.7(2); AsF, -7.9(3); AsCl, 27.2(4); AsH(2), 39.8(4); AsF(2), -96.6(9); AsCl(2), -17.8(10); AsH(3), 17.1(4); AsF(3)-196.0(5) and AsCl(3), -59.1(27) kcal mole(-1). These values are anchored only on one thermodynamic quantity, namely, ΔH(f)(Ø)(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 3d(10) electrons were computed explicitly in both RCCSD(T) and UCCSD(T)-F12 calculations with additional tight basis functions designed for As 3d(10) 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.
Authors:
Daniel K W Mok; Edmond P F Lee; Foo-Tim Chau; John M Dyke
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2011-4-13
Journal Detail:
Title:  Physical chemistry chemical physics : PCCP     Volume:  -     ISSN:  1463-9084     ISO Abbreviation:  -     Publication Date:  2011 Apr 
Date Detail:
Created Date:  2011-4-13     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  100888160     Medline TA:  Phys Chem Chem Phys     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong. bcdaniel@polyu.edu.hk epl@soton.ac.uk.
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