Department of Physics, Dalian Maritime University, Dalian, China 116026.
J Phys Chem A. 2009 Dec 31;113(52):14664-9. doi: 10.1021/jp9044379.
The dissociation rate constants for hydrogen fluoride dimers are calculated using the YL method, proposed by Yao and Lin (Yao, L.; Mebel, A. M.; Lu, H. F.; Neusser, H. J.; Lin, S. H. J. Phys. Chem. A 2007, 111, 6722). The dividing surface method and RRKM theory are also used to obtain pseudo-transition states and rate constants, respectively. For the dissociation of HF dimers, the anharmonic rate constants are around 3.02 x 10(10) to 3.46 x 10(12) s(-1), while the harmonic rate constants are in the range of 2.93 x 10(10) to 1.66 x 10(13) s(-1), at a temperature range of 243-1000 K, for the canonical case. For the microcanonical case, the anharmonic rate constants are in the range of 1.91 x 10(12) to 1.32 x 10(13) s(-1) and the harmonic rate constants are in the range of 1.89 x 10(12) to 4.93 x 10(13) s(-1), with a total energy range of 1338-4500 cm(-1). Both harmonic and anharmonic rate constants are only comparable to the experimental results 0.5 x 10(10) s(-1) and 1 x 10(11) s(-1) in an inert gas bath at room temperature. In this case the harmonic and anharmonic rate constants show similar results in this calculation. The results of this paper indicate that the YL method is suitable for calculating dissociation rate constants of small flexible HF dimers and the anharmonic effect should be included.
使用姚和林（Yao, L.; Mebel, A. M.; Lu, H. F.; Neusser, H. J.; Lin, S. H.）提出的 YL 方法计算氟化氢二聚体的离解速率常数。还使用划分表面方法和 RRKM 理论分别获得准过渡态和速率常数。对于 HF 二聚体的离解，非谐速率常数约为 3.02 x 10(10)至 3.46 x 10(12) s(-1)，而谐速率常数在 243-1000 K 的温度范围内处于 2.93 x 10(10)至 1.66 x 10(13) s(-1)的范围内，对于正则情况。对于微正则情况，非谐速率常数在 1.91 x 10(12)至 1.32 x 10(13) s(-1)的范围内，谐速率常数在 1.89 x 10(12)至 4.93 x 10(13) s(-1)的范围内，总能量范围为 1338-4500 cm(-1)。在室温惰性气体浴中，谐与非谐速率常数仅与实验结果 0.5 x 10(10) s(-1)和 1 x 10(11) s(-1)可比。在这种情况下，谐与非谐速率常数在该计算中显示出相似的结果。本文的结果表明，YL 方法适用于计算小的柔性 HF 二聚体的离解速率常数，并且应该包括非谐效应。
