应用化学2009，Vol.26Issue(12)：1484-1488,5.
密度泛函法计算C_1-C_(14)正构烃生成焓及C-C键裂解能
Enthalpies of Formation and C-C Bond Dissociation Energies of C_1-C_(14) Alkanes and Alkyl Radicals Calculated via Density Functional Theory Methods
摘要
Abstract
Enthalpies of formation and bond dissociation energies(BDE) of n-alkanes and the corresponding radicals of up to 14 carbons, involved in pyrolysis of Fischer-Tropsch naphtha were calculated using various density functional theory(DFT) methods. It was found that the MPW1B95/6-311G(d,p) method was the best in term of accuracy among the methods evaluated, including B97-1, BB1K, B1B95, MPWB1K and MPW1B95. On the basis of this good performance, the MPW1B95/6-311G(d,p) method was used for the estimation of large n-alkanes and their resulting radicals. C-C BDEs of n-alkanes were also examined. The enthalpies of formation of n-alkanes and the radicals had deviations of 0.8 and 2.7 kJ/mol respectively compared with experimental data. For C-C BDEs of n-alkanes, this method predicted the results with a mean absolute deviation of 3.1 kJ/mol. It is noted that by means of the MPW1B95/6-311G(d,p) method the enthalpies of formation can be calculated satisfactorily and the C-C BDEs and their change trend can be predicted reasonably.关键词
密度泛函/键解离能/生成焓/烃/自由基Key words
density functional theory/bond dissociation energy/enthalpy of formation/n-alkane/alkyl radical分类
化学化工引用本文复制引用
王峰,任杰,李永旺..密度泛函法计算C_1-C_(14)正构烃生成焓及C-C键裂解能[J].应用化学,2009,26(12):1484-1488,5.基金项目
国家杰出青年科学基金(20625620)资助项目 （20625620）
