摘要
采用密度泛函理论B3LYP方法研究了二氯硅烯(Si Cl2)自由基和异硫氰酸(HNCS)的反应机理。在6-311++G**基组水平上对反应物、中间体和过渡态进行了全几何参数优化,并通过频率分析和内禀反应坐标(IRC)确定各反应通道中的中间体和过渡态,再用QCISD(T)方法计算了各个驻点的单点能。计算结果表明:单重态的Si Cl2与HNCS有插入N-H键和C-N键的反应路径,其中经由三元环插入C-N键的反应通道反应势垒最低,是主反应通道。该反应主产物为Si Cl2NHCS。
The reaction mechanism of dichlorosilylene with isothiocyanic acid is investigated through B3LYP method of density function theory,and the geometries and harmonic of reactants,intermediates, transition states and products is calculated at the B3LYP/6-311++G**level.To obtain more precise energy result,the stationary point energies are calculated at QCISD( T)/6-311++G**//B3LYP /6-311 ++G**level.Intermediates and transition states are confirmed by the results of vibration analysis and the Intrinsic Reaction Coordinates ( IRC) calculation.The results indicate that the reaction of singlet state dichlorosilylene with isothiocyanic acid has the insertion N-H and C-N channel,respectively.The pathway HNCS+SiCl2→IM2→TS2→IM3→TS3→P1 is the main one with the lowest activation energy, and the main products are SiCl2 NHCS.
出处
《陇东学院学报》
2015年第1期52-55,共4页
Journal of Longdong University
基金
甘肃省应用化学省级重点学科建设项目(GSACKS20130113)
甘肃省自然科学基金(1208RTZM289)
庆阳市科技计划项目(KA201302)
关键词
二氯硅烯
异硫氰酸
反应机理
活化能
过渡态
dichlorosilylene
isothiocyanic acid
reaction mechanism
activation energy
transition state
