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首页> 外文期刊>Physical chemistry chemical physics: PCCP >Reply to the 'Comment on 'On the high pressure rate constants for the H/Mu + O_2 addition reactions'' by L. B. Harding, J. Troe and V. G. Ushakov, Phys. Chem. Chem. Phys., 2001, 3, 2630
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Reply to the 'Comment on 'On the high pressure rate constants for the H/Mu + O_2 addition reactions'' by L. B. Harding, J. Troe and V. G. Ushakov, Phys. Chem. Chem. Phys., 2001, 3, 2630

机译：L. B. Harding，J. Troe和V. G. Ushakov，Phys。答复“关于“关于H / Mu + O_2加成反应的高压速率常数”的评论”。化学化学物理学。，2001，3，2630

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Concerning the Comment by Harding, Troe and Ushakov (HTU) on our recent Communication, we emphasize the following points. First, the authors explain the differences in the H + O_2 capture rates based on the differences between the DMBE IV potential energy surface and their own ab initio calculations along the minimum energy path (MEP). Clearly, Fig. 1 and Fig 2. of ref. 1 show that such a path results from a fit to ab initio points having a somewhat irregular behavior, especially in the asymptotic region. Although the reasons for this behavior are not clarified, one should have in mind possible crossings and avoided crossings, and the fact that ab initio calculations (especially in the long range interaction region) suffer from the basis set superposition error, which can be significant when using correlated levels of ab initio theory. Of course, exact ab initio results can be achieved only at full configuration interaction level with a complete basis set. Thus, at least for the reported H-O_2 distances (≥5.5 a_0), the differences (≤0.25 kcal mol~(-1); see Fig. 2 of ref. 1) between the DMBE IV potential energy surface and the MRCI calculations based on an aug-cc-pvtz basis set are probably within the error expected for state of the art calculations in polyatomic systems such as that in the title.
机译：关于哈丁，特洛和乌沙科夫（HTU）对我们最近的来文的评论，我们强调以下几点。首先，作者基于DMBE IV势能面与他们沿最小能量路径（MEP）的从头算起之间的差异，解释了H + O_2捕获速率的差异。显然，参考文献的图1和图2。图1示出了这样的路径是由于拟合到具有一些不规则行为的从头开始点而产生的，特别是在渐近区域中。尽管这种行为的原因尚不清楚，但应该记住可能的交叉，避免交叉，并且从头算起（尤其是在长距离交互作用区域中）的计算会遭受基集叠加误差的影响，当发生这种情况时，这可能很重要。使用相关级别的从头算理论。当然，只有在具有完整基础集的完整配置交互级别下，才能获得准确的从头开始的结果。因此，至少对于所报告的H-O_2距离（≥5.5a_0），DMBE IV势能面与MRCI计算之间的差异（≤0.25kcal mol〜（-1）;参见参考文献1的图2）。基于aug-cc-pvtz基集的数据可能在多原子系统（如标题中）的最新技术计算预期的误差之内。

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