论文标题
时间依赖性的密度功能理论协议，用于共振非弹性X射线散射计算
A time-dependent density functional theory protocol for resonant inelastic X-ray scattering calculations
论文作者
论文摘要
我们提出了一种基于时间依赖性的密度功能理论（TDDFT）方法，用于计算相对于共同基态的激发态的两个不同流形之间的光 - 耦合。这些量是解决Kramers的必要成分 - Heisenberg方程，以使谐振非弹性X射线散射（RIX）和其他几种类型的两光子光谱镜。该过程基于伪波函数方法，在该方法中，TDDFT本征态被视为与单个激发的构型相互作用波函数，以及在受限的能量窗口方法上，可以根据占用的分子轨道涉及涉及的激发过程的能量来严格定义激发态的流动状态。我们通过计算三个代表性氟尼族配合物的2P4D RIX图来说明该方法的适用性，并将其与实验结果进行比较。该方法能够准确地捕获所有三个复合物中的所有实验特征，相对能量在0.6 eV之内正确，成本为两个独立的TDDFT计算。
We present a time-dependent density functional theory (TDDFT) based approach to compute the light-matter couplings between two different manifolds of excited states relative to a common ground state. These quantities are the necessary ingredients to solve the Kramers--Heisenberg equation for resonant inelastic X-ray scattering (RIXS) and several other types of two-photon spectroscopies. The procedure is based on the pseudo-wavefunction approach, where TDDFT eigenstates are treated as a configuration interaction wavefunction with single excitations, and on the restricted energy window approach, where a manifold of excited states can be rigorously defined based on the energies of the occupied molecular orbitals involved in the excitation process. We illustrate the applicability of the method by calculating the 2p4d RIXS maps of three representative Ruthenium complexes and comparing them to experimental results. The method is able to accurately capture all the experimental features in all three complexes, with relative energies correct to within 0.6 eV at the cost of two independent TDDFT calculations.
