Zarzycki P, Charmas R, Szabelski P
Department of Theoretical Chemistry, Faculty of Chemistry, Maria Curie-Skłodowska University, Maria Curie-Skłodowska Square 3, 20-031, Lublin, Poland.
J Comput Chem. 2004 Apr 15;25(5):704-11. doi: 10.1002/jcc.10419.
Adsorption of protons on a heterogeneous solid surface is modeled using the Monte Carlo (MC) simulation method. The surface of an oxide is assumed to consist of adsorption sites with pK assigned according to a quasi-Gaussian distribution. The influence of the electrostatic interactions combined with the energetic heterogeneity of the surface is examined and the MC results are compared with the predictions of the analytical 1-pK approach. The surface potential behavior is examined using both "experimental" MC results and "theoretical" results obtained from the application of 1-pK model. The results are compared qualitatively with experimental determination of the surface potential of metal oxide surfaces. They confirm that the relation between the surface potential and the pH of bulk solution should not be described by the Nernst equation but by the equation with the parameter linearly reducing Nerstian potential. The values of this parameter are examined with respect to degree of surface energetic heterogeneity and site density of the surface.
使用蒙特卡罗（MC）模拟方法对质子在非均匀固体表面的吸附进行建模。假设氧化物表面由根据准高斯分布分配了pK的吸附位点组成。研究了静电相互作用与表面能量非均匀性相结合的影响，并将MC结果与分析性单pK方法的预测结果进行了比较。使用“实验性”MC结果和应用单pK模型获得的“理论性”结果来研究表面电位行为。将结果与金属氧化物表面表面电位的实验测定进行定性比较。结果证实，表面电位与本体溶液pH值之间的关系不应由能斯特方程描述，而应由具有线性降低能斯特电位参数的方程描述。针对表面能量非均匀程度和表面位点密度对该参数的值进行了研究。
