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Energy Expression of the Chemical Bond Between Atoms in Hydrides and Oxides and Its Application to Materials Design

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The DV-Xα Molecular-Orbital Calculation Method

Abstract

Using energy density analysis, total energy is partitioned into the atomic energy densities of constituent elements. The atomization energy of each element is then evaluated by subtracting the atomic energy density from the energy of the isolated neutral atom. This recent approach to the energy expression is reviewed of the chemical bond between atoms in hydrides and oxides. For various hydrides, the atomization energies, ΔE H for H atom and ΔE M for metal atom, are evaluated and the ΔE H vs. ΔE M diagram called atomization energy diagram is made. All the hydrides including complex hydrides and metal hydrides can be located on this diagram, although there are significant differences in the nature of the chemical bond among them. Also, for hydrocarbons, C m H n , the atomization energy for carbon, ΔE C , increases linearly with the ratio of carbon number to hydrogen number, m/n, while keeping ΔE H constant. It is no longer needed for us to give expression for the C-C bond to be either single, or double or triple bond in C m H n . For metal oxides, the atomization energies, ΔE M for metal atom and ΔE O for O atom, reflect the average structure as well as the local structure. As a result, their values change with the overall density of binary metal oxides. For perovskite-type oxides, the ΔE O value increases by the phase transition from cubic to tetragonal phase, regardless of the tilting-type or the <100> displacement-type transition. One of the applications of this approach is the quantitative evaluation for the catalytic activities of metal oxides (e.g., Nb2O5) on the dehydrogenation reaction of magnesium hydride (MgH2), MgH2 → Mg + H2. The atomization energy concept will provide us a new clue to materials design, for example, catalysts design.

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Acknowledgments

The authors would like to express sincere thanks to the staff of the Computer Center, Institute for Molecular Science, Okazaki National Institute for the use of their supercomputers. This study is 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.

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Authors and Affiliations

  1. Toyota Physical and Chemical Research Institute, Nagakute, Aichi, 480-1192, Japan

    Masahiko Morinaga

  2. Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan

    Masahiko Morinaga & Hiroshi Yukawa

  3. Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, Okubo, Shinjuku-ku, Tokyo, 169-8555, Japan

    Hiromi Nakai

Authors
  1. Masahiko Morinaga
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  2. Hiroshi Yukawa
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  3. Hiromi Nakai
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Correspondence to Masahiko Morinaga .

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Editors and Affiliations

  1. Faculty of Engineering Dept. of Advanced Materials Science, Kagawa University, Takamatsu, Japan

    Tomohiko Ishii

  2. Faculty of Science, Fukuoka University, Johnan-ku, Fukuoka, Japan

    Hisanobu Wakita

  3. Department of Chemistry, Kwansei Gakuin University, Hyogo, Japan

    Kazuyoshi Ogasawara

  4. Korea Basic Science Institute, Suncheon, Korea, Republic of (South Korea)

    Yang-Soo Kim

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Morinaga, M., Yukawa, H., Nakai, H. (2015). Energy Expression of the Chemical Bond Between Atoms in Hydrides and Oxides and Its Application to Materials Design. In: Ishii, T., Wakita, H., Ogasawara, K., Kim, YS. (eds) The DV-Xα Molecular-Orbital Calculation Method. Springer, Cham. https://doi.org/10.1007/978-3-319-11185-8_7

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