AI 中文总结
本研究通过第一性原理计算，首次系统证实常压下元素锰的三种晶相均具有自旋选择性非范德华电子化物特性，揭示了间隙阴离子电子的存在及其对低能电子结构的贡献，为开发非常规电子与磁性功能材料提供了新方向。
AI 中文摘要
电子化物是一类特殊的离子材料，其中定域在非原子核间隙区域的电子在晶格中充当阴离子。本文采用第一性原理量子力学计算，研究了元素锰（Mn）在常压（0 GPa）下的结构、电子、磁性及电子化物特性，重点关注其三种晶相：立方（α）-Mn（I4̄3m，编号217）、立方（β）-Mn（P4₁32，编号213）和六方（hex）-Mn（P6₃/mmc，编号194）。计算结果表明，三种晶相均表现出显著的间隙电子特性，同时伴随自旋选择性电子定域函数（ELF），由此确立元素锰为非范德华电子化物体系。Bader电荷分析显示，大量电子从锰主体骨架重新分布至间隙阴离子电子（IAE）区域，α-Mn、β-Mn和hex-Mn中每个间隙盆的有效电荷转移分别约为-1.645e、-1.477e和-1.083e。电子态密度进一步证实了其电子化物特性：与IAE相关的态在费米能级（E_F）附近存在有限贡献，且与锰衍生的态共存，表明它们直接参与低能电子结构。因此，电子定域函数（ELF）、有效电荷转移以及费米能级处IAE引起的电子布居共同为元素锰中的间隙阴离子电子提供了一致证据。据我们所知，本工作首次系统识别了常压下元素锰的自旋选择性电子化物特性，凸显了利用其间隙电子态实现非常规电子和磁性功能的可能性。
英文摘要
Electrides are an unusual class of ionic materials in which electrons localized in non-nuclear, interstitial regions act as anions within the crystal lattice. Here, we employ first-principles quantum mechanical calculations to investigate the structural, electronic, magnetic, and electride characteristics of elemental manganese (Mn) at an ambient pressure (0 GPa), focusing on its three crystalline phases: cubic ($α$)-Mn ($I\bar{4}3m,no.217$), cubic ($β$)-Mn ($P4_132, no.213$), and hexagonal ($hex$)-Mn ($P6_3/mmc, no.194$). Our calculations reveal pronounced interstitial-electron character in all three phases, accompanied by spin-selective electron localization function (ELF), establishing elemental Mn as a non-van der Waals electride system. Bader charge analysis indicates substantial electron redistribution from the Mn host framework toward the interstitial anionic-electron (IAE) regions, with an effective charge transfer of approximately $-1.645e$, $-1.477e$, and $-1.083e$ per interstitial basin in $α$-Mn, $β$-Mn, and $hex$-Mn, respectively. The electride character is further supported by the electronic density of states, where the IAE-associated states exhibit finite contributions near the Fermi level ($E_F$) and coexist with Mn-derived states, demonstrating their direct participation in the low-energy electronic structure. The combined electron localization function (ELF), effective charge transfer, and electron population due to IAE at $E_F$ therefore provide consistent evidence for interstitial anionic electrons in elemental Mn. To the best of our knowledge, this work provides the first systematic identification of spin-selective electride character in elemental Mn at ambient pressure, highlighting the possibility of exploiting its interstitial-electron states for unconventional electronic and magnetic functionalities.
