论文标题
电子亲和力时间依赖性密度功能理论：形式主义和对核心兴奋状态的应用
Electron-Affinity Time-Dependent Density Functional Theory: Formalism and Applications to Core-Excited States
论文作者
论文摘要
粒子 - 孔相互作用问题在时间依赖性密度功能理论（TDDFT）中长期存在，并导致K-EDGE X射线吸收光谱（XAS）的预测中造成极端误差。我们得出了一种线性反应形式主义，该形式使用使用N-1电子系统的优化轨道作为参考，建筑轨道放松以及在初始密度的适当孔。我们的方法是对静态交换近似的确切概括，可以减轻与绝热近似相关的粒子孔相互作用误差，并通过数量级减少TDDFT XAS中的误差。在仅0.5 eV的根平方误差和与TDDFT相同的计算缩放下，在核心价分离近似情况下，我们预计这种方法在大型系统的XAS计算中将具有很大的实用性。
The particle-hole interaction problem is longstanding within time-dependent density functional theory (TDDFT) and leads to extreme errors in the prediction of K-edge X-ray absorption spectra (XAS). We derive a linear-response formalism that uses optimized orbitals of the n-1-electron system as reference, building orbital relaxation and a proper hole into the initial density. Our approach is an exact generalization of the static-exchange approximation that ameliorates particle-hole interaction error associated with the adiabatic approximation and reduces errors in TDDFT XAS by orders of magnitude. With a statistical performance of just 0.5 eV root-mean-square error and the same computational scaling as TDDFT under the core-valence separation approximation, we anticipate that this approach will be of great utility in XAS calculations of large systems.
