Fisicaro G, Genovese L, Andreussi O, Marzari N, Goedecker S
Department of Physics, University of Basel, Klingelbergstrasse 82, 4056 Basel, Switzerland.
University of Grenoble Alpes, CEA, INAC-SP2M, L_Sim, F-38000 Grenoble, France.
J Chem Phys. 2016 Jan 7;144(1):014103. doi: 10.1063/1.4939125.
The computational study of chemical reactions in complex, wet environments is critical for applications in many fields. It is often essential to study chemical reactions in the presence of applied electrochemical potentials, taking into account the non-trivial electrostatic screening coming from the solvent and the electrolytes. As a consequence, the electrostatic potential has to be found by solving the generalized Poisson and the Poisson-Boltzmann equations for neutral and ionic solutions, respectively. In the present work, solvers for both problems have been developed. A preconditioned conjugate gradient method has been implemented for the solution of the generalized Poisson equation and the linear regime of the Poisson-Boltzmann, allowing to solve iteratively the minimization problem with some ten iterations of the ordinary Poisson equation solver. In addition, a self-consistent procedure enables us to solve the non-linear Poisson-Boltzmann problem. Both solvers exhibit very high accuracy and parallel efficiency and allow for the treatment of periodic, free, and slab boundary conditions. The solver has been integrated into the BigDFT and Quantum-ESPRESSO electronic-structure packages and will be released as an independent program, suitable for integration in other codes.
在复杂潮湿环境中对化学反应进行计算研究对于许多领域的应用至关重要。在存在外加电化学势的情况下研究化学反应通常必不可少，同时要考虑来自溶剂和电解质的非平凡静电屏蔽。因此，必须分别通过求解中性和离子溶液的广义泊松方程和泊松 - 玻尔兹曼方程来确定静电势。在本工作中，已开发出针对这两个问题的求解器。已实现一种预处理共轭梯度法来求解广义泊松方程和泊松 - 玻尔兹曼方程的线性区域，通过普通泊松方程求解器进行大约十次迭代即可迭代求解最小化问题。此外，一种自洽过程使我们能够求解非线性泊松 - 玻尔兹曼问题。这两种求解器都具有非常高的精度和并行效率，并允许处理周期性、自由和平板边界条件。该求解器已集成到BigDFT和Quantum - ESPRESSO电子结构软件包中，并将作为一个独立程序发布，适合集成到其他代码中。
