A Computational Study of C-S Bond Dissociation Enthalpies in Petroleum Chemistry

作者：Shi Jing; Hu Xi Rui; Liang Shuang^*

来源：Heteroatom Chemistry, 2011, 22(2): 97-105.

DOI：10.1002/hc.20662

High-level theoretical methods (BMK, B3LYP, B98, B3P86, B3PW91, PBE1PBE, PBE1KIS, MPWPW91, MPW1KCIS, TPSS1KCIS, G3, G3//BMK, and CBS-Q) were utilized to study the carbon-sulfur bond dissociation enthalpies (BDEs) of hydrocarbons in petroleum chemistry. The performance of these methods was evaluated on the basis of a training set including the available experimental BDEs, and it was found that the BMK (Boese-Martin for Kinetics) method had the best agreement with experimental values. By using the BMK method to calculate C-S BDEs of saturated hydrocarbon, the main factors, which determine the changing trend of BDE values, were discussed. Results revealed that the repulsive energies played an important role in determining a change in the trend of BDEs as well as the radical effect. Good agreements were obtained between further calculated BDEs and the experimental ones for C-S and C-O bonds. Moreover, the same calculation method was applied to predict C-S BDEs for which the experimental values were still unavailable. A range of predicted bond dissociation enthalpy values were provided according to the calculations.

• 出版日期2011
• 单位南开大学