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A non-empirical calculation of 2p core-electron excitation in compounds with 3d metal transition ions by ligand-field and density functional theory (LFDFT)

Abstract

Methodological advents for the calculation of the multiplet energy levels arising from multiple-open-shell 2p53dn+1 electron configuration, with n = 0, 1, 2, … and 9, are presented. We use the Ligand-Field Density Functional Theory (LFDFT) program, which has been recently implemented in the Amsterdam Density Functional (ADF) program package. The methodology consists of calculating the electronic structure of a central metal ion together with its ligand coordination by means of Density Functional Theory code. Besides, the core-hole effects are treated by incorporating many body effects and corrections via configuration interaction algorithm within the active space of Kohn-Sham orbitals with dominant 2p and 3d characters of the metal transition ions, using an effective ligand-field Hamiltonian. The Slater-Condon integrals (F2(3d,3d), F4(3d,3d), G1(2p,3d), G3(2p,3d) and F2(2p,3d)), spin-orbit coupling constants (ζ2p and ζ3d) and parameters of the ligand-field potential (represented within the Wybourne formalism) are therefore determined giving rise to the multiplet structures of systems with 3dn and 2p53dn+1 configurations. The oscillator strengths of the electric-dipole allowed 3dn → 2p53dn+1 transitions are also calculated allowing the theoretical simulation of the absorption spectra of the 2p core-electron excitation. The methodology is applied to metal transition ions in the series Sc2+, Ti2+, …, Ni2+ and Cu2+ but also to selective compounds, namely SrTiO3 and MnF2. The comparison with available experimental data is good. Therefore, a non-empirical ligand-field treatment of the 2p53dn+1 configuration is established and available in the ADF program package illustrating the spectroscopic details of the 2p core-electron excitation that can be valuable in the further understanding and interpretation of the transition metal L2,3-edges X-ray absorption spectra.

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Publication details

The article was received on 11 May 2017, accepted on 13 Jul 2017 and first published on 13 Jul 2017


Article type: Paper
DOI: 10.1039/C7CP03140H
Citation: Phys. Chem. Chem. Phys., 2017, Accepted Manuscript
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    A non-empirical calculation of 2p core-electron excitation in compounds with 3d metal transition ions by ligand-field and density functional theory (LFDFT)

    H. Ramanantoanina and C. Daul, Phys. Chem. Chem. Phys., 2017, Accepted Manuscript , DOI: 10.1039/C7CP03140H

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