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采用直接动力学方法,对化学反应NO+OClO的反应微观机理进行了理论研究.在MP2/6-311+G(d,p)水平下优化得到了稳定点的几何构型,并进行了简谐振动频率分析.通过应用内禀反应坐标理论获得了反应的最小能量路径,能量信息的较高水平的矫正在MC-QCISD//MP2/6-311+G(d,p)水平下完成.通过采用改进正则变分过渡态理论,同时结合小曲率隧道效应等校正方法,计算了得到了NO+OClO反应的速率常数值(298～2 000 K温度范围),理论计算得到的NO+OClO反应的速率常数值与实验数据符合得非常好.
A direct kinetic method was used to study the microscopic mechanism of chemical reaction of NO + OClO.The geometry of the stable point was optimized at the level of MP2 / 6-311 + G (d, p) The harmonic frequency analysis was performed by using the intrinsic reaction coordinate theory to obtain the minimum energy path of the reaction, and the higher level of correction of energy information was completed at the level of MC-QCISD // MP2 / 6-311 + G (d, p). The rate constants of NO + OClO reaction (298 ~ 2000 K) were calculated by using the modified regular variation transition state theory and the correction method such as small curvature tunneling effect. The calculated NO + OClO reaction The rate constants agree well with the experimental data.