Thermochemistry of 35 selected sulfur compounds, a comparison between experimented and theory

SULFUROS INORGANICOS

TERMOQUIMICA

QUIMICA TEORICA

QUIMICA DE COMBUSTION

CALCULOS DE REFERENCIA

2008

BIBLIOGRAFÍA NACIONAL QUÍMICA

The thermochemistry of 35 diatomic, triatomic and tetratomic, sulphur-containing molecules was investigated. For each molecule, we have estimated its enthalpy of formation at the CCSD(T)/CBS level, including corrections for, scalar relativistic, core-valence and spin-orbit effects. When experimental data was available we also included a correction for anharmonicities in Zero point energies. The molecules investigated are involved in several areas, atmospherical chemistry, astrochemsitry, nanotechnology, and biology. The present results demonstrate that from the previous landmark review of Benson, published in 1978, we had advanced only a little and much work must be done to have sulfur thermochemistry well established. It was very difficult to obtain a meaningful mean absolute deviation (MAD) because of the reduced number of accurate enthalpies of formation available. For a selected set of eight molecules the MAD=0.4 kcal/mol. For the 27 remaining molecules we discussed the available experimental and theoretical data and suggested new values. The consistency of our propositions has been double checked employing homodesmic and isodesmic reactions. In all cases, except one that involved S2, the results were perfectly consistent. We expect that the present work motivates new theoretical and experimental investigations of these fascinating species that contain sulfur.

Journal of Sulfur Chemistry v. 29, no. 3-4, 2008. -- p. 327-352

Taylor, Francis Online

2008

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DOI: 10.1080/17415990802047352