多种密度泛函方法计算碳氧单键解离能的性能比较  

The comparison among various density functional theory methods applied to the computation of C—OH single bond dissociation energy

作　　者：杨忠志[1] 刘林林[1] 

机构地区：[1]辽宁师范大学化学化工学院,辽宁大连116029

出　　处：《辽宁师范大学学报（自然科学版）》2015年第1期66-71,共6页Journal of Liaoning Normal University:Natural Science Edition

基　　金：国家自然科学基金项目(21073080;21133005)

摘　　要：运用当前发展的40种密度泛函方法对30种包含碳氧单键C-OH的有机物中碳氧单键的解离能进行理论计算,并将获得的理论值与已知实验值进行比较,发现BMK和MPW1B95两种密度泛函方法用于碳氧单键解离能的计算所得到的结果相对可靠,而TPSSLYP1W密度泛函方法计算出来的结果与实验获得的数值之间呈现出最大的偏差.我们对造成这种差异的原因进行了进一步地分析,发现拟合密度泛函方法时所采用的数据集及参考性质,对其所适用的化合物范围及性质的表征有至关重要的影响.这为今后使用理论方法对实验无法获得准确碳氧单键解离能数值的化合物中的碳氧键断裂难易程度的表征,提供了一定的参考价值.Forty density functional methods were employed to calculate C-OH bond dissociation energies of thirty compounds containing C-OH single bonds. Theoretical bond dissociation energies were compared with the experimental values available in order to confirm the suitability of these methods. It is found that BMK and MPWlB95 methods have a comparable reliable performance. The TPSSLYPlW presents the largest derivation among all the methods. Further analysis shows that the data sets and properties applied to the fitting of the density functional methods are vital to the performance. This provides some reference for the characterization of the compounds containing C-OH single bonds whose experimental bond dissociation energies are unavailable.

关 键 词：密度泛函理论 键解离能 零点能校正 从头计算 BMK 

分 类 号：O641.121[理学—物理化学]