TY - JOUR
T1 - Energy expression of the chemical bond between atoms in metal oxides
AU - Shinzato, Yoshifumi
AU - Saito, Yuki
AU - Yoshino, Masahito
AU - Yukawa, Hiroshi
AU - Morinaga, Masahiko
AU - Baba, Takeshi
AU - Nakai, Hiromi
N1 - Funding Information:
The authors would like to express sincere thanks to the staffs of the Computer Center, Institute for Molecular Science, Okazaki National Institute for the use of super-computers. This study was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology of Japan, and by the Japan Society for the Promotion of Science and also by the 21st Century COE program “Nature-Guided Materials Processing” of the Ministry of Education, Culture, Sports, Science and Technology of Japan. One of the authors (Y. Shinzato) was supported by Research Fellowship of the JSPS for Young Scientists.
PY - 2011/7
Y1 - 2011/7
N2 - The chemical bond between atoms in metal oxides is expressed in an energy scale. Total energy is partitioned into the atomic energy densities of constituent elements in the metal oxide, using energy density analysis. The atomization energies, ΔEM for metal atom and ΔE O for O atom, are then evaluated by subtracting the atomic energy densities from the energy of the isolated neutral atom, M and O, respectively. In this study, a ΔEO vs. ΔEM diagram called atomization energy diagram is first proposed and used for the understanding of the nature of chemical bond in various metal oxides. Both ΔEM and ΔEO values reflect the average structure as well as the local structure. For example their values vary depending on the vertex, edge or face sharing of MO6 octahedron, and also change with the overall density of binary metal oxides. For perovskite-type oxides it is shown that the ΔEO value tends to increase by the phase transition from cubic to tetragonal phase, regardless of the tilting-type or the 〈1 0 0〉 displacement-type transition. The bond formation in spinel-type oxides is also understood with the aid of the atomization energies. The present approach based on the atomization energy concept will provide us a new clue to the design of metal oxides.
AB - The chemical bond between atoms in metal oxides is expressed in an energy scale. Total energy is partitioned into the atomic energy densities of constituent elements in the metal oxide, using energy density analysis. The atomization energies, ΔEM for metal atom and ΔE O for O atom, are then evaluated by subtracting the atomic energy densities from the energy of the isolated neutral atom, M and O, respectively. In this study, a ΔEO vs. ΔEM diagram called atomization energy diagram is first proposed and used for the understanding of the nature of chemical bond in various metal oxides. Both ΔEM and ΔEO values reflect the average structure as well as the local structure. For example their values vary depending on the vertex, edge or face sharing of MO6 octahedron, and also change with the overall density of binary metal oxides. For perovskite-type oxides it is shown that the ΔEO value tends to increase by the phase transition from cubic to tetragonal phase, regardless of the tilting-type or the 〈1 0 0〉 displacement-type transition. The bond formation in spinel-type oxides is also understood with the aid of the atomization energies. The present approach based on the atomization energy concept will provide us a new clue to the design of metal oxides.
KW - A. Oxides
KW - C. Ab initio calculations
KW - D. Electronic structure
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U2 - 10.1016/j.jpcs.2011.03.014
DO - 10.1016/j.jpcs.2011.03.014
M3 - Article
AN - SCOPUS:79957700524
SN - 0022-3697
VL - 72
SP - 853
EP - 861
JO - Journal of Physics and Chemistry of Solids
JF - Journal of Physics and Chemistry of Solids
IS - 7
ER -