烃类化合物碳氢键解离焓的密度泛函理论研究CHBond.pdfVIP

2008 年第 28 卷 有 机 化 学 Vol. 28, 2008 第 3 期, 459～466 Chinese Journal of Organic Chemistry No. 3, 459～466 ·研究论文· 烃类化合物碳氢键解离焓的密度泛函理论研究 郑文锐 傅 尧* 王华静 郭庆祥* ( 中国科学技术大学化学系 合肥 230026) 摘要 通过比较 10 种密度泛函方法对烃类化合物碳氢键解离焓的计算精度, 发现新型密度泛函 BMK 方法具有最高的 计算精度. 利用该方法计算了包含饱和链烃,、不饱和链烃、脂环烃和芳香烃在内的 172 个烃类化合物的碳氢键解离焓, 计算均方根误差仅为 7.95 kJ •mol－1, 线性拟合常数为 0.985. 通过自然键轨道法分析发现, 烃类物质的碳氢键解离焓与 母体的碳氢键杂化轨道成分 p %, 自由基奇电子轨道杂化成分p %及自由基的自旋密度三个参数之间存在较好的定量关 系. 此外, 饱和链烷烃及不饱和链烃的碳氢键解离焓与碳氢键键长之间也存在较好的线性关系. 关键词 键解离焓; 密度泛函方法; 自然键轨道分析; 烃类化合物 C—H Bond Dissociation Enthalpies of Hydrocarbons by Density Functional Theory Studies ZHENG, Wen-Rui FU, Yao* WANG, Hua-Jing GUO, Qing-Xiang* (Department of Chemistry , University of Science and Technology of China, Hefei 230026) Abstract Ten density functional theory (DFT) methods were compared for calculating the car- bon-hydrogen bond dissociation energies of hydrocarbons. It was found that the newly developed DFT method BMK gave the best results. Subsequently the carbon-hydrogen bond dissociation enthalpies of 172 hydrocarbons including alkanes, unsaturated chain hydrocarbons, alicyclic hydrocarbons and aromatic hy- drocarbons were calculated systematically using the BMK method. The root of mean square error was as low －1 as 7.95 kJ•mol and the correlation coefficient was 0.985. The natural bond orbital (NBO) analysis revealed that the C—H bond dissociation enthalpies (BDEs) of hydrocarbons were dependent on the hybridiz