Wang Ru-Pan, Liu Boyang, Green Robert J, Delgado-Jaime Mario Ulises, Ghiasi Mahnaz, Schmitt Thorsten, van Schooneveld Matti M, de Groot Frank M F
Inorganic Chemistry & Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
Department of Physics & Astronomy, University of British Columbia, V6T 1Z1 Vancouver, British Columbia, Canada.
J Phys Chem C Nanomater Interfaces. 2017 Nov 16;121(45):24919-24928. doi: 10.1021/acs.jpcc.7b06882. Epub 2017 Oct 27.
We show that with 2p3d resonant inelastic X-ray scattering (RIXS) we can accurately determine the charge-transfer parameters of CoF, CoCl, CoBr, and CoS. The 160 meV resolution RIXS results are compared with charge-transfer multiplet calculations. The improved resolution and the direct observation of the crystal field and charge-transfer excitations allow the determination of more accurate parameters than could be derived from X-ray absorption and X-ray photoemission, both limited in resolution by their lifetime broadening. We derive the crystal field and charge-transfer parameters of the Co ions, which provides the nature of the ground state of the Co ions with respect to symmetry and hybridization. In addition, the increased spectral resolution allows the more accurate determination of the atomic Slater integrals. The results show that the crystal field energy decreases with increasing ligand covalency. The L edge RIXS spectra show that the intensity of the (Coster-Kronig induced) nonresonant X-ray emission is a measure of ligand covalency.
我们表明，利用2p3d共振非弹性X射线散射（RIXS），我们能够准确测定CoF、CoCl、CoBr和CoS的电荷转移参数。将160毫电子伏特分辨率的RIXS结果与电荷转移多重态计算结果进行了比较。分辨率的提高以及对晶体场和电荷转移激发的直接观测，使得我们能够确定比X射线吸收和X射线光电子能谱更准确的参数，后两者都因寿命展宽而在分辨率上受到限制。我们推导了Co离子的晶体场和电荷转移参数，这提供了Co离子基态在对称性和杂化方面的性质。此外，更高的光谱分辨率使得能够更准确地测定原子斯莱特积分。结果表明，晶体场能量随着配体共价性的增加而降低。L边RIXS光谱表明，（由科斯特-克勒尼希效应引起的）非共振X射线发射强度是配体共价性的一种度量。
