Rossmeisl Jan, Nørskov Jens K, Taylor Christopher D, Janik Michael J, Neurock Matthew
Center for Atomic-scale Materials Physics, NanoDTU, Department of Physics, Technical University of Denmark, DK-2800 Lyngby, Denmark.
J Phys Chem B. 2006 Nov 2;110(43):21833-9. doi: 10.1021/jp0631735.
Ab initio density functional theory is used to calculate the electrochemical phase diagram for the oxidation and reduction of water over the Pt(111) surface. Three different schemes proposed in the literature are used to calculate the potential-dependent free energy of hydrogen, water, hydroxyl, and oxygen species adsorbed to the surface. Despite the different foundations for the models and their different complexity, they can be directly related to one another through a systematic Taylor series expansion of the Nernst equation. The simplest model, which includes the potential only as a shift in the chemical potential of the electrons, accounts very well for the thermochemical features determining the phase-diagram.
从头算密度泛函理论用于计算铂（111）表面上水氧化和还原的电化学相图。文献中提出的三种不同方案用于计算吸附在表面的氢、水、羟基和氧物种的电位依赖自由能。尽管模型的基础不同且复杂度各异，但它们可以通过能斯特方程的系统泰勒级数展开直接相互关联。最简单的模型仅将电位视为电子化学势的偏移，能很好地解释决定相图的热化学特征。
