J. Nucl. Phy. Mat. Sci. Rad. A.

Atomic Multiplet and Charge Transfer Effects in the Resonant Inelastic X-Ray Scattering (RIXS) Spectra at the Nickel L2,3 Edge of NiF2

J Jiménez-Mier P Olalde-Velasco, P De La Mora, W-L Yang, and J Denlinger

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Core-level spectroscopies. RIXS, Nickel difluoride, Electronic structure

PUBLISHED DATE August 07, 2017
PUBLISHER The Author(s) 2017. This article is published with open access at www.chitkara.edu. in/publications

Resonant inelastic x-ray scattering (RIXS) is used to study the electronic structure of NiF2, which is the most ionic of the nickel compounds. RIXS can be viewed as a coherent two-steps process involving the absorption and the emission of x-rays. The soft x-ray absorption spectrum (XAS) at the metal L2,3 edge indicate the importance of atomic multiplet effects. RIXS spectra at L2,3 contain clearly defined emission peaks corresponding to d-excited states of Ni2+ at energies few eV below the elastic emission, which is strongly suppressed. These results are confirmed by atomic multiplet calculations using the Kramers-Heisenberg formula for RIXS processes. For larger energy losses, the emission spectra have a broad charge-transfer peak that results from the decay of hybridized Ni(3d)-F(2p) valence states. This is confirmed by comparison of the absorption and emission spectra recorded at the nickel L and fluorine K edges with F p and Ni d partial density of states using LDA + U calculations.

Page(s) pp. 1–13
URL http://dspace.chitkara.edu.in/jspui/bitstream/1/861/3/51001_JNP_JIMENEZ.pdf
ISSN 2321-8649
DOI https://doi.org/10.15415/jnp.2017.51001
  • Becke, A.D. & Johnson, E.R. (2006) A simple effective potential for exchange. J. Chem. Phys. 24, #221101.
  • Blaha, P. et al. WIEN2k an Augmented Plane Wave Plus Local Orbital Program for Calculating Crystal Properties, Vienna University of Technology, Vienna, 2001.
  • Chiuzb˘aian, S. G. et al. (2005) Localized Electronic Excitations in NiO Studied with Resonant Inelastic X-Ray Scattering at the Ni M Threshold: Evidence of Spin Flip. Phys. Rev. Lett. 95, #197402
  • Cowan, R.D. (1981). The Theory of Atomic Structure and Spectra, Berkeley: University of California Press.
  • Dagotto, E. (2005) Complexity in Strongly Correlated Electronic Systems, Science 309, 257–262.
  • Dufek, P., Schwarz, K. & Blaha, P. (1993) Electronic structure of MnF2 and NiF2, Phys. Rev. B 48, 12672–12681.
  • Ghiringhelli, G. et al. (2009) Observation of Two Nondispersive Magnetic Excitations in NiO by Resonant Inelastic Soft-X-Ray Scattering, Phys. Rev. Lett. 102, #027401.
  • Godby, R., Schlu¨ter, M. & Sham, L. (1986) Accurate Exchange-Correlation Potential for Silicon and Its Discontinuity on Addition of an Electron. Phys. Rev. Lett. 56, 2415–2418.
  • de Groot, F. & Kotani, A. (2008) Core Level Spectroscopy of Solids, Boca Raton, Fl, CRC Press.
  • de Groot, F. (2001) High-Resolution X-ray Emission and X-ray Absorption Spectroscopy. Chemistry Review 101, 1779–1808.
  • de Groot, F. (2005) Multiplet effects in X-ray spectroscopy. Coordination Chemistry Reviews 249, 31–63.
  • Imada, M., Fujimori, A. & Tokura, Y. (1998) Metal-insulator transitions, Rev. Mod. Phys. 70, 1039–1263.
  • Jia, J.J. et al. (1995) First experimental results from IBM/TENN/TULANE/ LLNL/LBL undulator beamline at the advanced light source. Rev. Sci. Instrum. 66, 1394–1397.
  • Jiménez-Mier, J., Ederer, D.L. & Schuler, T. (2005) X-ray Raman scattering at the manganese L edge of MnF2: Valence emission of Mn2+. Phys. Rev. A 72, #022502.
  • van der Laan, G. et al. (1986) Comparison of X-ray absorption with x-ray photoemission of nickel diahlides and NiO, Phys. Rev. B, 33, 4253–4263.
  • Lee, D. H. et al. (2012) Conversion mechanism of nickel fluoride and NiO-doped nickel fluoride in Li ion batteries. Electrochimica Acta 59, 213–221.
  • Lee, D.H. et al. (2014) Understanding improved electrochemical properties of NiO-doped NiF2- C composite conversion materials by X-ray absorption spectroscopy and pair distribution function analysis, Phys. Chem. Chem. Phys. 16, 3095–3102.
  • Olalde-Velasco, P. et al. (2011) Direct probe of Mott-Hubbard to charge-transfer insulator transition and electronic structure evolution in transition-metal systems, Phys. Rev B. 83, #241102(R).
  • Olalde-Velasco, P., Jiménez-Mier, J., Denlinger, J., & Yang, W.-L. (2013) Atomic multiplets at the L2,3 edge of 3d transition metals and the ligand K edge in x-ray absorption spectroscopy of ionic systems, Phys. Rev. B 87, #245136.
  • Perdew J.P., Burke, K & Ernzerhof, M. (1996) Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 77, 3865–3868.
  • Stavitski, E. & de Groot, F.M.F. (2008) The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges. Micron 41, 687–694.
  • Tran, F. & Blaha, P. (2009) Accurate Band Gaps of Semiconductors and Insulators with a Semilocal Exchange-Correlation Potential. Phys. Rev. Lett. 102, #226401.
  • Yang, L., Luo, W. & Chen, G.-Z. (2013) In Situ Synthesis of Ni(o) Catalysts Derived from Nickel Halides for Hydrolytic Dehy-drogenation of Ammonia Borane. Catalysis Letters, 143, 873–880.
  • Yang, Y. et al. (2014) Flexible Three-Dimensional Nanoporous Metal-Based Energy Devices. J. Am. Chem. Soc. 136, 6187–6190.
  • Zaanen, J., Sawatzky, G.A. & Allen, J.W. (1985) Band Gaps and Electronic Structure of Transition-Metal Compounds, Phys. Rev. Lett. 55, 418–421.
  • Zhang, H., Zhou, Y,-N., Sun, Q., & Fu, Z,-W. (2008) Nanostructured nickel fluoride thin film as a new Li storage material, Solid State Sciences 10, 1166–1172.