Max-Planck-Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470 Mülheim an der Ruhr, Germany.
Phys Chem Chem Phys. 2013 Feb 28;15(8):2712-24. doi: 10.1039/c2cp42675g.
The proper description of electrified metal/solution interfaces, as they occur in electrochemical systems, is a key component for simulating the unique features of electrocatalytic reactions using electronic structure calculations. While in standard solid state (plane wave, periodic boundary conditions) density functional theory (DFT) calculations several models for describing electrochemical environments exist, for cluster models in a quantum chemistry approach (atomic orbital basis, finite system) this is not straightforward. In this work, two different approaches for the theoretical description of electrified interfaces of nanoparticles, the constant charge and the constant potential model, are discussed. Different schemes for describing electrochemical reactions including solvation models are tested for a consistent description of the electrochemical potential and the local chemical behavior for finite structures. The different schemes and models are investigated for the oxygen reduction reaction (ORR) on a hemispherical cuboctahedral platinum nanoparticle.
电化学反应系统中，金属/溶液界面的准确描述是利用电子结构计算模拟电催化反应独特特征的关键组成部分。在标准固态（平面波，周期性边界条件）密度泛函理论（DFT）计算中，存在几种用于描述电化学环境的模型，但对于量子化学方法中的团簇模型（原子轨道基，有限体系），这并不简单。在这项工作中，讨论了两种用于理论描述纳米颗粒带电界面的不同方法，即恒电荷模型和恒电势模型。测试了不同的描述电化学反应的方案，包括溶剂化模型，以实现对有限结构的电化学势和局部化学行为的一致描述。针对半球形八面体铂纳米颗粒上的氧还原反应（ORR），研究了不同的方案和模型。
