Josefsson Ida, Kunnus Kristjan, Schreck Simon, Föhlisch Alexander, de Groot Frank, Wernet Philippe, Odelius Michael
†Department of Physics, Stockholm University, AlbaNova University Center, 106 91 Stockholm, Sweden.
‡Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Strasse 15, 12489 Berlin, Germany.
J Phys Chem Lett. 2012 Dec 6;3(23):3565-70. doi: 10.1021/jz301479j. Epub 2012 Nov 26.
A new ab initio approach to the calculation of X-ray spectra is demonstrated. It combines a high-level quantum chemical description of the chemical interactions and local atomic multiplet effects. We show here calculated L-edge X-ray absorption (XA) and resonant inelastic X-ray scattering spectra for aqueous Ni(2+) and XA spectra for a polypyridyl iron complex. Our quantum chemical calculations on a high level of accuracy in a post-Hartree-Fock framework give excellent agreement with experiment. This opens the door to reliable and detailed information on chemical interactions and the valence electronic structure in 3d transition-metal complexes also in transient excited electronic states. As we combine a molecular-orbital description with a proper treatment of local atomic electron correlation effects, our calculations uniquely allow, in particular, identifying the influence of interatomic chemical interactions versus intra-atomic correlations in the L-edge X-ray spectra.
展示了一种计算X射线光谱的从头算新方法。它结合了对化学相互作用和局部原子多重态效应的高水平量子化学描述。我们在此展示了计算得到的水合Ni(2+)的L边X射线吸收（XA）和共振非弹性X射线散射光谱以及一种聚吡啶铁配合物的XA光谱。我们在Hartree-Fock后框架下进行的高精度量子化学计算与实验结果高度吻合。这为获取关于3d过渡金属配合物中化学相互作用和价电子结构的可靠且详细的信息打开了大门，即使是在瞬态激发电子态下也是如此。由于我们将分子轨道描述与对局部原子电子相关效应的适当处理相结合，我们的计算尤其独特地能够确定L边X射线光谱中原子间化学相互作用与原子内相关性的影响。
