Intra- and inter-atomic optical transitions of Fe, Co, and Ni ferrocyanides studied using first-principles many-electron calculations
- Department of Materials, Physics and Energy Engineering, Graduated School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan)
- Department of Crystalline Materials Science, Graduated School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan)
- Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-16 O-okayama, Meguro-ku, Tokyo 152-8550 (Japan)
We have investigated the electronic structures and optical properties of Fe, Co, and Ni ferrocyanide nanoparticles using first-principles relativistic many-electron calculations. The overall features of the theoretical absorption spectra for Fe, Ni, and Co ferrocyanides calculated using a first-principles many-electron method well reproduced the experimental one. The origins of the experimental absorption spectra were clarified by performing a configuration analysis based on the many-electron wave functions. For Fe ferrocyanide, the experimental absorption peaks originated from not only the charge-transfer transitions from Fe{sup 2+} to Fe{sup 3+} but also the 3d-3d intra-transitions of Fe{sup 3+} ions. In addition, the spin crossover transition of Fe{sup 3+} predicted by the many-electron calculations was about 0.24 eV. For Co ferrocyanide, the experimental absorption peaks were mainly attributed to the 3d-3d intra-transitions of Fe{sup 2+} ions. In contrast to the Fe and Co ferrocyanides, Ni ferrocyanide showed that the absorption peaks originated from the 3d-3d intra-transitions of Ni{sup 3+} ions in a low-energy region, while from both the 3d-3d intra-transitions of Fe{sup 2+} ions and the charge-transfer transitions from Fe{sup 2+} to Ni{sup 3+} in a high-energy region. These results were quite different from those of density-functional theory (DFT) calculations. The discrepancy between the results of DFT calculations and those of many-electron calculations suggested that the intra- and inter-atomic transitions of transition metal ions are significantly affected by the many-body effects of strongly correlated 3d electrons.
- OSTI ID:
- 22596816
- Journal Information:
- Journal of Applied Physics, Vol. 119, Issue 23; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-8979
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
GENERAL PHYSICS
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ABSORPTION
ABSORPTION SPECTRA
COBALT
DENSITY FUNCTIONAL METHOD
ELECTRONIC STRUCTURE
ELECTRONS
FERROCYANIDES
IRON IONS
MANY-BODY PROBLEM
NANOPARTICLES
NICKEL IONS
OPTICAL PROPERTIES
PEAKS
SPIN
WAVE FUNCTIONS