Electronic structure calculations of oxidation reactions on nanoporous gold

本科学提案致力于阐明模型auu合金表面甲醇全部氧化和部分氧化的详细机理，以及模型AuAg和AuCu合金表面丙烯氧化的详细机理。沿着这些路线，将获得纳米孔金上复杂化学过程的原子洞察力。关键反应中间体的理论预测，它们的吸附几何形状，结合强度，振动频率，以及STM图像的建模将支持实验数据的分析和解释。特别是，我们将提供反应性的机制描述（作为ad-metal浓度的函数以及氧、OH和水的活性形式）和基于电子结构计算的关键反应步骤的速率常数。我们的DFT和高度精确的从头计算丙烯氧化将与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.