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介绍了一个包括隧道效应和曲率校正的单分子热反应速率常数的计算程序,该程序以微正则速率常数为基础,通过积分的方法求得热速率常数。同时考虑量子力学隧道校正和垂直于反应途径(IRC)的振动与沿IRC的运动之间的耦合作用(曲率校正)。通过对氟代乙炔氢迁移反应和二氟代乙炔氟迁移反应的速率常数研究,得到的结果与国际通用程序POLYRATE得到的结果相一致,数据吻合较好,且可以节省较多的计算量。
A calculation procedure for the rate constant of a single molecule thermal reaction including tunneling and curvature correction is presented. The program calculates the thermal rate constant by integral method based on the micro-regressive rate constant. Consider both the quantum mechanics tunnel correction and the coupling (curvature correction) between the vibration perpendicular to the reaction path (IRC) and the movement along the IRC. Through the study on the rate constants of fluoroacetylene migration and difluoroacetylene migration, the obtained results are in good agreement with those obtained by POLYRATE. The data agree well with each other, and the computational cost can be saved.