Kroll Thomas, Solomon Edward I, de Groot Frank M F
Department of Chemistry, Stanford University , Stanford, California 94305, United States.
Department of Inorganic Chemistry and Catalysis, Utrecht University , Universiteitsweg 99, 3584 CG Utrecht, Netherlands.
J Phys Chem B. 2015 Oct 29;119(43):13852-8. doi: 10.1021/acs.jpcb.5b04133. Epub 2015 Aug 13.
A projection method to determine the final-state configuration character of all peaks in a charge transfer multiplet calculation of a 2p X-ray absorption spectrum is presented using a d(0) system as an example. The projection method is used to identify the most important influences on spectral shape and to map out the configuration weights. The spectral shape of a 2p X-ray absorption or L2,3-edge spectrum is largely determined by the ratio of the 2p core-hole interactions relative to the 2p3d atomic multiplet interaction. This leads to a nontrivial spectral assignment, which makes a detailed theoretical description of experimental spectra valuable for the analysis of bonding.
以d(0)系统为例，提出了一种在2p X射线吸收光谱的电荷转移多重态计算中确定所有峰的终态构型特征的投影方法。该投影方法用于识别对光谱形状的最重要影响，并绘制出构型权重。2p X射线吸收光谱或L2,3边缘光谱的形状在很大程度上由2p芯孔相互作用与2p3d原子多重态相互作用的比率决定。这导致了一个复杂的光谱归属，这使得对实验光谱进行详细的理论描述对于键合分析很有价值。
