Function-Space-Based Solution Scheme for the Size-Modified Poisson-Boltzmann Equation in Full-Potential DFT.
Function-Space-Based Solution Scheme for the Size-Modified Poisson-Boltzmann Equation in Full-Potential DFT.
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DOI：
10.1021/acs.jctc.6b00435
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发表时间：
2016-06
影响因子：
5.5
通讯作者：
Stefan Ringe;H. Oberhofer;C. Hille;S. Matera;K. Reuter
中科院分区：
文献类型：
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作者：
Stefan Ringe;H. Oberhofer;C. Hille;S. Matera;K. Reuter
尺寸修正泊松-玻尔兹曼（MPB）方程是一种有效的隐式溶剂化模型，也能捕捉到电解溶剂效应。它结合了介质溶剂响应与溶剂化有限尺寸离子的平均场描述的帐户。本文提出了一种基于快速面向函数空间的牛顿法和格林函数预条件迭代线性解的MPB方程通解方案。与流行的多网格求解器相比，这种方法允许我们充分利用专门的集成网格和优化的集成方案。我们描述了全势密度泛函理论（DFT）代码FHI-aims的相应的数值高效实现。我们表明，加上额外的Stern层校正，DFT+MPB方法可以描述KCl水溶液在很宽浓度范围内的平均活度系数。计算出的活度系数对所采用的离子参数具有很高的灵敏度，因此建议采用广泛制表的盐溶液实验活度系数作为系统的参数化方案。
The size-modified Poisson-Boltzmann (MPB) equation is an efficient implicit solvation model which also captures electrolytic solvent effects. It combines an account of the dielectric solvent response with a mean-field description of solvated finite-sized ions. We present a general solution scheme for the MPB equation based on a fast function-space-oriented Newton method and a Green's function preconditioned iterative linear solver. In contrast to popular multigrid solvers, this approach allows us to fully exploit specialized integration grids and optimized integration schemes. We describe a corresponding numerically efficient implementation for the full-potential density-functional theory (DFT) code FHI-aims. We show that together with an additional Stern layer correction the DFT+MPB approach can describe the mean activity coefficient of a KCl aqueous solution over a wide range of concentrations. The high sensitivity of the calculated activity coefficient on the employed ionic parameters thereby suggests to use extensively tabulated experimental activity coefficients of salt solutions for a systematic parametrization protocol.