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气相单分子反应是目前反应动力学中研究得最为透彻的一个领域。在单分子反应动力学中,较为成功的二个理论是RRK(Rice-Ramsperger-Kassel)和RRKM(R-R-K-Marcus)理论。由于这二个理论在计算反应的速度常数时均较为繁琐,故在实际应用时必须借助计算机解决。本文给出用RRKM理论和量子化的RRK理论(即QRRK)计算处于不同能级的单分子微观反应速度常数的程序。同时也给出在应用RRKM时,及在微观分子动力学中极为有用的计算分子态密度的程序(Whitten-Rabinovitch近似方法)。作为应用的举例,我们根据QRRK理论,给出在激光多光子解离过程中,求每个分子平均吸收光子数与解离率的程序。
Gas phase monomolecular reaction is the most thoroughly studied reaction kinetics in the field. In the single-molecule reaction kinetics, two successful theories are the RRK (Rice-Ramsperger-Kassel) and the RRKM (R-R-K-Marcus) theory. Since these two theories are relatively complicated when calculating the velocity constants of the reaction, they must be solved by computer in practice. This paper presents a procedure for calculating the single-molecule microscopic reaction rate constants at different energy levels using the RRKM theory and the quantized RRK theory (ie QRRK). The Whitten-Rabinovitch approximation method, which is extremely useful in the application of RRKM and in microscopic molecular dynamics, is also given. As an application example, according to the QRRK theory, we give the procedure of finding the average absorbed photons and dissociation rate of each molecule in the process of laser multiphoton dissociation.