带电界面局部响应理论的屏蔽有效电荷方法
Local Response Theory of Electrified Interfaces from Screened Effective Charges
- Fritz-Haber-Institut der Max-Planck-Gesellschaft（马克斯·普朗克学会弗里茨·哈伯研究所）
机构由 AI 辅助整理，请以论文原文为准。
AI总结：
本文提出屏蔽电化学玻恩有效电荷（SEBEC），建立带电界面的局部响应理论，实现全局响应的无歧义分解，并推广至结构弛豫、电容及斯塔克调谐分析。
AI中文摘要：
第一性原理电子结构模拟能够直接获取基态全局系统性质。在计算电化学领域，这些性质包括依赖偏压的能量、自由能、功函数和电容等。然而，关于这些量如何通过界面充电对偏压做出响应的系统性局部描述仍然缺失。在此，我们引入了屏蔽电化学玻恩有效电荷（SEBEC），这是一种混合总能导数，用于测量在电化学边界条件下原子自由度对界面充电的力响应。SEBEC在电化学中的作用类似于玻恩有效电荷在现代极化理论中的作用：它们提供了全局响应的无歧义分解，并生成了与固态响应理论中熟悉的结构弛豫、电容和电化学斯塔克调谐相同的正式结构。更广泛的意义在于，这一局部响应框架使电化学界面更接近绝缘固体早已确立的概念严谨性。
英文摘要：
First-principles, electronic-structure simulations provide direct access to ground-state, global system properties. In the context of computational electrochemistry these are, e.g., bias-dependent energies, free energies, work functions, and capacitances. However, a comparably systematic local description of how these quantities respond to biasing via interfacial charging is still missing. Here, we introduce the screened electrochemical Born effective charge (SEBEC), a mixed total-energy derivative that measures the force response of an atomic degree of freedom to interfacial charging under electrochemical boundary conditions. SEBECs play the role for electrochemistry that Born effective charges play in the modern theory of polarization: they provide an unambiguous decomposition of global response and generate the same formal structures for structural relaxation, capacitance, and electrochemical Stark tuning that are familiar from solid-state response theory. The broader implication is a local response framework that brings electrochemical interfaces closer to the conceptual rigor long established for insulating solids.
