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利用密度泛函方法(B3LYP)在6-311+G(d,p)基组水平上研究了CH3SCH3与CHnF3-n(n=0～3)吸氢反应的微观动力学机理,在QCISD(T)/6-311G(d,p)//B3LYP/6-311+G(d,p)+ZPE水平上进行了单点能校正,并利用Polyrate 8.2程序计算了各反应在200～3000K温度区间内的速率常数kTST、kCVT和kCVT/SCT,此外运用酸碱软硬度理论解释了随着甲基自由基逐步被F取代,速率常数不呈规律性变化的原因。
The micro-kinetic mechanism of the hydrogen absorption reaction of CH3SCH3 with CHnF3-n (n = 0 ~ 3) was studied at the 6-311 + G (d, p) basis by density functional theory (B3LYP) ) / 6-311G (d, p) // B3LYP / 6-311 + G (d, p) + ZPE and the Polyrate 8.2 program was used to calculate the reaction temperature in the range of 200 ~ 3000K Within the rate constants kTST, kCVT and kCVT / SCT, in addition to the use of acid-base soft hardness theory explains the gradual substitution of methyl radicals with F, the rate constant does not regular change causes.