Max-Planck-Institute for Chemical Energy Conversion, Stiftstraße 34-36, D-45470 Mülheim an der Ruhr, Germany.
Beilstein J Nanotechnol. 2014 May 20;5:668-76. doi: 10.3762/bjnano.5.79. eCollection 2014.
In order to simulate electrochemical reactions in the framework of quantum chemical methods, density functional theory, methods can be devised that explicitly include the electrochemical potential. In this work we discuss a Grand Canonical approach in the framework of density functional theory in which fractional numbers of electrons are used to represent an open system in contact with an electrode at a given electrochemical potential. The computational shortcomings and the additional effort in such calculations are discussed. An ansatz for a SCF procedure is presented, which can be applied routinely and only marginally increases the computational effort of standard constant electron number approaches. In combination with the common implicit solvent models this scheme can become a powerful tool, especially for the investigation of omnipresent non-faradaic effects in electrochemistry.
为了在量子化学方法的框架内模拟电化学反应，可以设计出明确包含电化学势的方法。在这项工作中，我们讨论了密度泛函理论框架中的巨正则方法，其中使用分数电子数来表示与给定电化学势的电极接触的开放系统。讨论了此类计算中的计算缺点和额外工作。提出了一个 SCF 程序的假设，该假设可以常规应用，并且仅略微增加标准恒定电子数方法的计算工作量。与常见的隐式溶剂模型结合使用，该方案可以成为一种强大的工具，特别是对于研究电化学中普遍存在的非法拉第效应。
