Ab Initio Molecular Dynamics Calculations versus Quantum-State-Resolved Experiments on CHD3 + Pt(111): New Insights into a Prototypical Gas-Surface Reaction
Ab Initio Molecular Dynamics Calculations versus Quantum-State-Resolved Experiments on CHD3 + Pt(111): New Insights into a Prototypical Gas-Surface Reaction
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DOI：
10.1021/jz500233n
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发表时间：
2014-04-17
影响因子：
5.7
通讯作者：
Kroes, Geert-Jan
中科院分区：
文献类型：
--
作者：
Nattino, Francesco;Ueta, Hirokazu;Kroes, Geert-Jan
甲烷在金属表面上的解离化学吸附具有基础和实际意义，是蒸汽重整过程中的限速步骤。该反应最好通过量子动力学计算进行建模，但目前不能保证产生准确的结果，因为它们依赖于基于未经测试的密度泛函和未经测试的动力学近似的势能表面。为了帮助克服这些限制，我们在这里首次展示了通过从头分子动力学 (AIMD) 获得的多原子气相分子与金属表面反应的统计准确的反应概率。使用通用密度泛函，AIMD 反应概率与 CHID3 + Pt(111) 上的新量子态解析实验半定量一致。比较表明，尽管 CHD3 具有较大的旋转常数并且 CH4 + Pt(111) 的估计反应势垒为 0.9 eV，但仍可使用突然近似来处理旋转。
The dissociative chemisorption of methane on metal surfaces is of fundamental and practical interest, being a rate-limiting step in the steam reforming process. The reaction is best modeled with quantum dynamics calculations, but these are currently not guaranteed to produce accurate results because they rely on potential energy surfaces based on untested density functionals and on untested dynamical approximations. To help overcome these limitations, here we present for the first time statistically accurate reaction probabilities obtained with ab initio molecular dynamics (AIMD) for a polyatomic gas-phase molecule reacting with a metal surface. Using a general purpose density functional, the AIMD reaction probabilities are in semiquantitative agreement with new quantum-state-resolved experiments on CHID3 + Pt(111). The comparison suggests the use of the sudden approximation for treating the rotations even though CHD3 has large rotational constants and yields an estimated reaction barrier of 0.9 eV for CH4 + Pt(111).