Rusanova Maria Yu, Tsirlina Galina A, Nazmutdinov Renat R, Fawcett W Ronald
Department of Chemistry, University of California, Davis, California 95616, USA.
J Phys Chem A. 2005 Feb 24;109(7):1348-56. doi: 10.1021/jp046917s.
The effect of charge distribution within Cr(III) and Eu(III) aquacomplexes on the kinetics of simple electron-transfer reactions at electrodes is considered. The construction of corrected Tafel plots using noninteger effective charges for the reactant and product estimated on the basis of quantum-chemical data was shown to be more reasonable than the traditional approach in which integer charges are assumed. The potential distribution near the electrode has been estimated both by the Gouy-Chapman model and from Monte Carlo simulations for 1-1 supporting electrolytes. Kinetic parameters obtained using the two approaches are compared.
考虑了Cr(III)和Eu(III)水配合物中电荷分布对电极上简单电子转移反应动力学的影响。结果表明，基于量子化学数据估算反应物和产物的非整数有效电荷来构建校正的塔菲尔图，比传统的假设整数电荷的方法更为合理。通过 Gouy-Chapman 模型和针对1-1支持电解质的蒙特卡罗模拟估算了电极附近的电位分布。比较了使用这两种方法获得的动力学参数。
