摘要
应用量子化学从头算和密度泛函理论(DFT),对3CH2自由基与SO分子反应的单、三重态势能面进行了研究.在UB3LYP/6-311G(d,p)水平上优化了反应通道上各驻点(反应物、中间体、过渡态和产物)的几何构型.在CCSD(T)/6-311G(d,p)水平上计算了各物种的单点能,并对总能量进行了零点能校正.研究结果表明:主要的反应通道都在单重态势能面中,反应物中自由基3CH2的C原子进攻SO分子中的O原子是主要的进攻方式,反应主产物是P1(HS+HCO).反应热为-349.06kJ?mol-1.
Using the ab initio calculation and density functional theory methods, the singlet and triplet potential energy surfaces of the ^3CH2＋SO reaction were studied. At the UB3LYP/6-311G（d,p） level, the geometries of all species （reactants, intermediates, transition states and products） were optimized, while all the energies of the species were obtained with the correction of ZPVE at the CCSD（T）/6-311G（d,p） level. The calculated results indicate that all the major pathways of the reaction were obtained on the singlet potential energy surface. It is shown that the C atom of ^3CH2 radical to attack O atom of SO molecule was the major attack form to yield the main product of （HS ＋HCO） with the reaction heat of -349.06 kJ·mol^-1.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2006年第2期139-144,共6页
Acta Chimica Sinica
基金
国家自然科学基金(No.20303007)
教育部骨干教师基金
吉林省杰出青年基金资助项目.
关键词
从头算
密度泛函理论
^3CH2自由基
反应通道
ab initio
density funtional theory
triplet methylene radical
reaction channel
