Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory
Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory
复制标题
DOI：
10.1021/jp803174m
复制
发表时间：
2008-12-18
影响因子：
2.9
通讯作者：
Neese, Frank
中科院分区：
文献类型：
--
作者：
George, Serena DeBeer;Petrenko, Taras;Neese, Frank
铁K边X射线吸收前边缘功能已被计算使用含时密度泛函方法。的功能，溶剂化，和相对论效应的影响计算的能量和强度已被检查的相关性的计算参数的实验数据上的一系列的10个铁模型络合物，它跨越了一系列的高自旋和低自旋亚铁和铁络合物的O-h到T-d的几何形状。计算了四极和偶极对光谱的贡献。我们发现，通过使用CP（PPP）基组上的Fe和TZVP的剩余原子之一的BP 86功能，得到了很好的理论和实验之间的协议。包含溶剂化产生一个小的改进，在计算的能量。然而，包含标量相对论效应并没有产生任何改善的相关性与实验。使用这些方法来唯一地分配个人的光谱跃迁，并检查实验的贡献backbonding进行了讨论。
Iron K-edge X-ray absorption pre-edge features have been calculated using a time-dependent density functional approach. The influence of functional, solvation, and relativistic effects on the calculated energies and intensities has been examined by correlation of the calculated parameters to experimental data on a series of 10 iron model complexes, which span a range of high-spin and low-spin ferrous and ferric complexes in O-h to T-d geometries. Both quadrupole and dipole contributions to the spectra have been calculated. We find that good agreement between theory and experiment is obtained by using the BP86 functional with the CP(PPP) basis set on the Fe and TZVP one of the remaining atoms. Inclusion of solvation yields a small improvement in the calculated energies. However, the inclusion of scalar relativistic effects did not yield any improved correlation with experiment. The use of these methods to uniquely assign individual spectral transitions and to examine experimental contributions to backbonding is discussed.