Electronic structure calculations of oxidation reactions on nanoporous gold

这一科学建议致力于阐明甲醇在模型AuCu合金表面上完全氧化和部分氧化的详细机理，以及在模型AuAg和AuCu合金表面上丙烯氧化的详细机理。沿着这些思路，将获得对纳米孔Au上复杂的化学过程的原子洞察。对关键反应中间体、它们的吸附几何结构、结合强度、振动频率的理论预测以及对STM图像的模拟将支持对实验数据的分析和解释。特别是，我们将提供基于电子结构计算的关键反应步骤的反应性(作为金属浓度以及氧、羟基和水的活性形式的函数)和速率常数的机理描述。我们对丙烯氧化的DFT和高精度从头计算将与AIMD模拟进行比较，以提供对潜在过程的完整理解。

This scientific proposal is devoted to elucidation of the detailed mechanisms involved in the total and partial oxidation of methanol on model AuCu alloy surfaces as well as the elucidation of the detailed mechanism involved in the oxidation of propylene on model AuAg and AuCu alloy surfaces. Along these lines, atomistic insight into complex chemical processes on nanoporous Au will be obtained. Theoretical prediction of the key reaction intermediates, their adsorption geometry, binding strengths, vibrational frequencies, as well as modeling of STM images will support the analysis and interpretation of experimental data. In particular, we will provide a mechanistic description of the reactivity (as a function of the ad-metal concentration and that of active forms of oxygen, OH and water) and rate constants of critical reaction steps calculated on the basis of electronic structure calculations. Our DFT and highly accurate ab initio calculations of the propylene oxidation will be compared to AIMD simulations to provide a complete understanding of the underlying processes.