新乡学院学报
新鄉學院學報
신향학원학보
Journal of Xinxiang University
2014年
10期
13-18
,共6页
密度泛函理论%极化模型%N-Nitrosulfonamide化合物%键离解能%取代基效应
密度汎函理論%極化模型%N-Nitrosulfonamide化閤物%鍵離解能%取代基效應
밀도범함이론%겁화모형%N-Nitrosulfonamide화합물%건리해능%취대기효응
density functional theory%polarized continuum model%N-Nitrosulfonamide compound%bond dissociation energy%substituent effects
利用B3LYP、B3PW91、B3P86、B1LYP、BMK、MPWB1K、PBE0、CBS‐4M 和 M06‐2X方法结合6‐311+ G (2d ,p)基组计算了N -NO2键离解能。将计算结果与实验值进行比较,结果表明BM K和B3P86方法与实验结果吻合较好,平均绝对偏差分别为2.0 kJ/mol和6.3 kJ/mol。B3LYP、B3PW91、B1LYP、MPWB1K和PBE0方法的计算结果比实验值低,且B3LYP、B3PW91、B1LYP、M06‐2X和CBS‐4M方法的计算结果得到的平均绝对偏差和最大偏差都比较大,因此不能准确计算N‐Nitrosulfonamide的N -NO2键离解能。利用BMK/6‐311+G(2d ,p)方法进一步研究了N‐Nitrosulfonamide化合物的取代基效应。自然键轨道分析表明在 lpN1→BD*(O1‐N2)的 E(2)和Hammett常数之间,键离解能和lpN1→BD*(O1‐N2)的 E(2)之间都存在较好的相关性。
利用B3LYP、B3PW91、B3P86、B1LYP、BMK、MPWB1K、PBE0、CBS‐4M 和 M06‐2X方法結閤6‐311+ G (2d ,p)基組計算瞭N -NO2鍵離解能。將計算結果與實驗值進行比較,結果錶明BM K和B3P86方法與實驗結果吻閤較好,平均絕對偏差分彆為2.0 kJ/mol和6.3 kJ/mol。B3LYP、B3PW91、B1LYP、MPWB1K和PBE0方法的計算結果比實驗值低,且B3LYP、B3PW91、B1LYP、M06‐2X和CBS‐4M方法的計算結果得到的平均絕對偏差和最大偏差都比較大,因此不能準確計算N‐Nitrosulfonamide的N -NO2鍵離解能。利用BMK/6‐311+G(2d ,p)方法進一步研究瞭N‐Nitrosulfonamide化閤物的取代基效應。自然鍵軌道分析錶明在 lpN1→BD*(O1‐N2)的 E(2)和Hammett常數之間,鍵離解能和lpN1→BD*(O1‐N2)的 E(2)之間都存在較好的相關性。
이용B3LYP、B3PW91、B3P86、B1LYP、BMK、MPWB1K、PBE0、CBS‐4M 화 M06‐2X방법결합6‐311+ G (2d ,p)기조계산료N -NO2건리해능。장계산결과여실험치진행비교,결과표명BM K화B3P86방법여실험결과문합교호,평균절대편차분별위2.0 kJ/mol화6.3 kJ/mol。B3LYP、B3PW91、B1LYP、MPWB1K화PBE0방법적계산결과비실험치저,차B3LYP、B3PW91、B1LYP、M06‐2X화CBS‐4M방법적계산결과득도적평균절대편차화최대편차도비교대,인차불능준학계산N‐Nitrosulfonamide적N -NO2건리해능。이용BMK/6‐311+G(2d ,p)방법진일보연구료N‐Nitrosulfonamide화합물적취대기효응。자연건궤도분석표명재 lpN1→BD*(O1‐N2)적 E(2)화Hammett상수지간,건리해능화lpN1→BD*(O1‐N2)적 E(2)지간도존재교호적상관성。
The assessment of the N -NO2 bond dissociation energies(BDEs) was performed by various calculating methods, B3LYP, B3PW91, B3P86, B1LYP, BMK, MPWB1K, PBE0, CBS‐4M and M06‐2X at 6‐311+G(2d, p) basis set .Compared with the experimental BDEs, the results show that BMK and B3P86 methods reproduce the ex‐perimental values well .The mean absolute deviations from the experimental values obtained by BMK and B3P86 methods were 2.0 and 6.3 kJ/mol, respectively .B3LYP, B3PW91, B1LYP, MPWB1K and PBE0 methods underes‐timated the homolytic N -NO2 BDEs .B3LYP, B3PW91, B1LYP, M06‐2X, CBS‐4M methods failed providing an ac‐curate description of N -NO2 BDEs for NNitrosulfonamide compounds and showed larger mean absolute deviations and maximum deviations .Further, substituent effect based on BMK/6‐311+G(2d, p) method was analyzed .Natural bond orbital analysis showed that there exists good linear correlations between E(2) of lpN1 → BD* (O1‐N2 ) and Ham‐mett constants and a better correlation between the BDEs and the second order stabilization energy E(2) of lpN1 →BD* (O1‐N2 ) .