Open AccessSystematic First-Principles Calculations of Charge Transfer Transitions of Transition Metal Ions (Sc3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+) in α-Al2O3 with Structural Optimization
Author(s) -
Shota Takemura,
Mega Novita,
Kazuyoshi Ogasawara
Publication year - 2020
Publication title -
iop conference series. materials science and engineering
Language(s) - English
Resource type - Journals
eISSN - 1757-899X
pISSN - 1757-8981
DOI - 10.1088/1757-899x/835/1/012005
Subject(s) - ion , atomic physics , castep , multiplet , transition metal , crystallography , physics , chemistry , materials science , electronic structure , spectral line , computational chemistry , biochemistry , astronomy , catalysis , quantum mechanics
In order to calculate the LMCT energies for various trivalent TM ions in α-Al 2 O 3 using realistic model clusters, we performed structural optimization using the CASTEP code and constructed the optimized TMO 6 9- and TMAl 13 O 6 30+ clusters (TM = Sc 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ ). We obtained the LMCT energies of TM ions by first-principles many-electron calculations using the DVME method. It was found that the differences between the LMCT energies of the optimized clusters and those of the relaxed clusters based on the crystal radii originate from the difference in the multiplet splitting of the LMCT states. The results also indicated that the LMCT energies of transition metal ions in α-Al 2 O 3 can be calculated using small clusters composed of the central TM ion and the first-neighbor oxygen ions.