Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory

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• 作者：Yu Zhang ; Shaul Mukamel ; Munira Khalil ; Niranjan Govind
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2015
• 出版时间：December 8, 2015
• 年：2015
• 卷：11
• 期：12
• 页码：5804-5809
• 全文大小：392K
• ISSN：1549-9626

文摘

Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a powerful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal鈥搇igand bonding character compared with conventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We consider seven low- and high-spin model complexes involving chromium, manganese, and iron transition metal centers. Our results are in good agreement with experiment.