Department of Chemistry, University of California, 1 Shields Avenue, Davis, CA 95616, USA.
J Synchrotron Radiat. 2013 Jul;20(Pt 4):614-9. doi: 10.1107/S0909049513003142. Epub 2013 May 30.
X-ray absorption and scattering spectroscopies involving the 3d transition-metal K- and L-edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M-edges, which are below 100 eV. Synchrotron-based X-ray sources can have higher energy resolution at M-edges. M-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) could therefore provide complementary information to K- and L-edge spectroscopies. In this study, M2,3-edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M2,3-edge RIXS on NiO, NiF2 and two other covalent complexes have been performed and different d-d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M-edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high-sensitivity and high-resolution superconducting tunnel junction X-ray detectors below 100 eV is also illustrated and discussed.
X 射线吸收和散射光谱学涉及 3d 过渡金属的 K 和 L 边缘，在研究无机和生物无机分子方面有着悠久的历史。然而，使用低于 100eV 的 M 边缘的研究非常少。基于同步加速器的 X 射线源在 M 边缘具有更高的能量分辨率。因此，M 边缘 X 射线吸收光谱学（XAS）和共振非弹性 X 射线散射（RIXS）可以为 K 和 L 边缘光谱学提供补充信息。在这项研究中，测量了几个 Co、Ni 和 Cu 配合物的 M2,3 边缘 XAS，并分析和讨论了它们的光谱信息，如化学位移和共价效应。此外，还对 NiO、NiF2 和另外两个共价配合物进行了 M2,3 边缘 RIXS，观察到了不同的 d-d 跃迁模式。虽然还处于初步阶段，但这项关于 3d 金属配合物的工作表明，未来有可能在更复杂的 3d 金属配合物上使用 M 边缘 XAS 和 RIXS。还说明了并讨论了在 100eV 以下使用高灵敏度和高分辨率超导隧道结 X 射线探测器的潜力。
