From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni2+ in Aqueous Solution with Resonant Inelastic X-ray Scattering

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• 作者：Kristjan Kunnus ; Ida Josefsson ; Simon Schreck ; Wilson Quevedo ; Piter S. Miedema ; Simone Techert ; Frank M. F. de Groot ; Michael Odelius ; Philippe Wernet ; Alexander F?hlisch
• 刊名：Journal of Physical Chemistry B
• 出版年：2013
• 出版时间：December 27, 2013
• 年：2013
• 卷：117
• 期：51
• 页码：16512-16521
• 全文大小：452K
• ISSN：1520-5207

文摘

Bonding of the Ni²⁺(aq) complex is investigated with an unprecedented combination of resonant inelastic X-ray scattering (RIXS) measurements and ab initio calculations at the Ni L absorption edge. The spectra directly reflect the relative energies of the ligand-field and charge-transfer valence-excited states. They give element-specific access with atomic resolution to the ground-state electronic structure of the complex and allow quantification of ligand-field strength and 3d鈥?d electron correlation interactions in the Ni²⁺(aq) complex. The experimentally determined ligand-field strength is 10Dq = 1.1 eV. This and the Racah parameters characterizing 3d鈥?d Coulomb interactions B = 0.13 eV and C = 0.42 eV as readily derived from the measured energies match very well with the results from UV鈥搗is spectroscopy. Our results demonstrate how L-edge RIXS can be used to complement existing spectroscopic tools for the investigation of bonding in 3d transition-metal coordination compounds in solution. The ab initio RASPT2 calculation is successfully used to simulate the L-edge RIXS spectra.