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

A non-empirical calculation of 2p core-electron excitation in

compounds with 3d metal transition ions by ligand-field and

density functional theory (LFDFT)

Harry Ramanantoanina*a _{and Claude Daul}b

a_{Paul Scherrer Institute, CH-5232 Villigen, Switzerland; E-mail: [email protected]} b_{Department of chemistry, University of Fribourg, Chemin du musée 9, CH-1700 Fribourg, Switzerland}

Fig. S1 LFDFT results of the 3d5 ₍6_S

5/2) → 2p53d6 (in green), 3d4 (5D0) → 2p53d5 (in blue) and 3d3 (4F3/2) → 2p53d4 (in red)

transitions of free Mn2+_{, Mn}3+ _{and Mn}4+ _{ions: Lorentzian convolution of the oscillator strengths of the electronic transitions}

with a half-width of half-maximum of 0.20 eV. The calculated parameters of the ligand field Hamiltonian are listed in Table 1.

Fig. S2 LFDFT results of the 3d5 ₍6_S

5/2) → 2p53d6 transitions of free Mn2+ ion obtained from DFT calculations employing

the LDA (in green), GGA (in black) and Hybrid (in red) functional: Lorentzian convolution of the oscillator strengths of the electronic transitions with a half-width of half-maximum of 0.20 eV. The calculated parameters of the ligand field Hamiltonian are listed in Table 1.

640

650

660

670

0

1

Fig. S3 Radial functions of the Kohn-Sham orbitals with dominant 3d characters of Mn2+ _{obtained for the 3d}5 _{(up, solid}

curves) and 2p5_3d6 _{(down, dashed curves) electron configurations in free ion (in black) and in (MnF}

6)4- embedded in MnF2

(in red and blue).

0 1 2 3 4 0.00 0.25 0.50 0.75 1.00 0 1 2 3 4 0.00 0.25 0.50 0.75 1.00

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