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利用密度泛函理论(B3LYP,B3PW91,B3P86),使用6-31G**基组计算了乙氰溶液中S-亚硝基硫醇化合物中S-NO的键离解能。结果表明B3PW91/6-31G**方法计算得出的键离解能平均绝对偏差为7.36 kJ/mol,与实验符合比较好。因此,我们建议使用B3PW91/6-31G**方法来计算S-亚硝基硫醇化合物中S-NO的键离解能。进一步分析表明不同的取代基对S-NO的键离解能影响不同。当C6H5SNO中的一个H基团分别被2-CH3、4-CH3、4-Cl、4-NO2基组取代时,S-NO的键离解能降低2.09~12.54 kJ/mol。当C6H5SNO中的一个H基团分别被2-Cl、3-CH3、3-Cl、4-OCH3基组取代时,S-NO的键离解能增加0.042~36.37 kJ/mol。
The bond dissociation energies of S-NO in S-nitrosothiol compounds in acetonitrile were calculated using the density functional theory (B3LYP, B3PW91, B3P86) using the 6-31G ** basis set. The results show that the average absolute deviation of bond dissociation energy calculated by the B3PW91 / 6-31G ** method is 7.36 kJ / mol, which is in good agreement with the experiment. Therefore, we propose to use the B3PW91 / 6-31G ** method to calculate the bond dissociation energies of S-NO in S-nitrosothiol compounds. Further analysis shows that different substituents can have different effects on the dissociation of S-NO bonds. When one H group in C6H5SNO was replaced by 2-CH3, 4-CH3, 4-Cl and 4-NO2 groups respectively, the bond dissociation of S-NO decreased by 2.09 ~ 12.54 kJ / mol. When one H group in C6H5SNO is substituted by 2-Cl, 3-CH3, 3-Cl, 4-OCH3 groups respectively, the bond dissociation of S-NO increases by 0.042-36.37 kJ / mol.