论文标题
投影的混合密度功能：核心电子电离的方法和应用
Projected Hybrid Density Functionals: Method and Application to Core Electron Ionization
论文作者
论文摘要
这项工作提出了一类新的杂化密度功能理论（DFT）近似值，并在预定义的状态（例如核心原子轨道（AOS））中纳入了非本地精确交换。这些预测的杂交密度功能是范围分离杂种的灵活概括。这项工作使用绝热投影形式主义得出了预测的杂种。一个人将电子电子相互作用算子投射到所选预定义的状态上，重新引入了投影的操作员到非互动的Kohn-Sham参考系统中，并引入了其余电子电子相互作用的密度函数近似。预计的混合动力很容易实现现有的密度功能代码，只需要投影单电子密度矩阵和交换运算符，输入现有例程。这项工作还提出了第一个应用程序：核心项目的Perdew-Burke-Ernzerhof混合PBE0C70，其中非局部精确交换的部分从核心AOS中的25％增加到70％。自动选择投影的AO提供了适合核心和价电子性能的黑盒模型化学反应。 PBE0C70预测了核心轨道能，这些核心轨道能准确地恢复了第二行元素和第三行元素的核心电子结合能，而不会降低PBE0的价值良好性能。
This work presents a new class of hybrid density functional theory (DFT) approximations, incorporating nonlocal exact exchange in predefined states such as core atomic orbitals (AOs). These projected hybrid density functionals are a flexible generalization of range-separated hybrids. This work derives projected hybrids using the Adiabatic Projection formalism. One projects the electron-electron interaction operator onto the chosen predefined states, reintroduces the projected operator into the noninteracting Kohn-Sham reference system, and introduces a density functional approximation for the remaining electron-electron interactions. Projected hybrids are readily implemented existing density functional codes, requiring only a projection of the one-electron density matrices and exchange operators entering existing routines. This work also presents a first application: a core-projected Perdew-Burke-Ernzerhof hybrid PBE0c70, in which the fraction of nonlocal exact exchange is increased from 25% to 70% in core AOs. Automatic selection of the projected AOs provides a black-box model chemistry appropriate for both core and valence electron properties. PBE0c70 predicts core orbital energies that accurately recover core-electron binding energies of second- and third-row elements, without degrading PBE0's good performance for valence-electron properties.
