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本文在几个由Persky等人最近得到的扩展-LEPS势上,用变分过渡态理论研究了Cl+H(D)Br、Br+H(D)I的动力学,计算了这些反应的速度常数、势能面瓶颈区性质和动力学同位素效应。我们对Cl+HBr和Cl+DBr反应的计算结果与Persky等在同样势能面上的QCT计算结果及现有的实验结果非常一致;因此,我们认为有关Cl+H(D)Br体系的这个新势能面可用于进一步的动力学计算。但本文对Br+H(D)I的VTST计算与实验和QCT计算差别较大,我们认为歧异的原因是有关Br+H(D)I体系的这个势能面不很理想,有可能它在鞍点附近未能重现真实势能面的性质,因此还需对其进一步鉴定和改进。
In this paper, the dynamics of Cl + H (D) Br, Br + H (D) I have been studied by using the variational transition state theory in several extended-LEPS potentials recently obtained by Persky et al. The rates of these reactions have been calculated Constraints on the nature of the bottleneck region and the kinetic isotopes of the constants, potential energy surfaces. Our calculated results for Cl + HBr and Cl + DBr are in good agreement with the results of QCT calculated by Persky et al. On the same potential surface and the existing experimental results. Therefore, we consider that this new (Cl + H (D) Potential energy surfaces can be used for further kinetic calculations. However, the calculation of VTST for Br + H (D) I is quite different from the experimental and QCT calculations. The reason for this discrepancy is that the potential energy surface of the Br + H (D) I system is not very ideal, Near the failure to reproduce the true nature of the potential energy surface, it needs to be further identified and improved.