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High-Dimensional Model Representation of Cyclic Voltammograms

机译:循环伏安图的高维模型表示

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Digital simulation costs present an obstacle on the way to high-speed, real-time, on-line theoretical analysis of experimental data in cyclic voltammetry. To overcome this difficulty, we propose to use solution mapping based on a correlated, hierarchical expansion of multivariate functions, known as high-dimensional model representation (HDMR). The nonlinear dependencies of the simulated voltammograms on multiple model parameters are represented in the form of compact look-up tables, from which approximate voltammograms can be calculated rapidly by interpolation, for any model parameter combinations from a predefined domain. Most importantly, the HDMR does not suffer from the problem of the exponential growth of the look-up tables with the number of model parameters. The creation of a solution map requires a single effort of simulating many voltammograms. However, once the map is prepared, it can be stored and reused many times without the need to repeat costly simulations. HDMR maps are created and examined for five examples of cyclic voltammetry models at planar macroelectrodes in a one-dimensional spatial geometry under pure diffusion transport conditions. The usefulness of the maps for rapid visualization and exploration of the effects of the parameters on the voltammograms and for rapid simultaneous estimation of many parameters from cyclic voltammetric data is demonstrated through computational experiments.
机译:数字仿真成本为循环伏安法中实验数据的高速,实时,在线理论分析提供了障碍。为了克服这个困难,我们建议使用基于多维函数的相关层次扩展的解决方案映射,称为高维模型表示(HDMR)。模拟的伏安图对多个模型参数的非线性依赖性以紧凑查找表的形式表示,对于预定义域中的任何模型参数组合,可以通过内插快速计算出近似伏安图。最重要的是,HDMR不会出现随着模型参数数量的增加而使查询表呈指数增长的问题。创建解决方案图只需要一次模拟许多伏安图的工作。但是,一旦准备好地图,便可以存储并重复使用许多次,而无需重复昂贵的模拟。在纯扩散传输条件下,以一维空间几何形状在平面宏电极上为五个示例的循环伏安模型创建HDMR图并对其进行检查。通过计算实验证明了该图对于快速可视化和探索参数对伏安图的影响以及从循环伏安数据快速同时估算许多参数的有用性。

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