Density functional theory analysis for orbital interaction between hypophosphite ions and metal surfaces

    研究成果: Article

    12 引用 (Scopus)

    抄録

    In order to elucidate the reactivity difference of hypophosphite ions used as reducing agents for electroless deposition on different metal surfaces, such as Pd and Cu, electronic structures of the activation states of hypophosphite ion oxidation on these surfaces were intensively analyzed by using Density Functional Theory (DFT). In the calculation, we focused on the dehydrogenation reaction which should be a rate-determining step in the elementary reaction steps. From the calculation results, a particular orbital interaction between the hypophosphite ion and the metal surface was observed. On Pd (111), the s-orbital of H in the hypophosphite ion interacts singly with the d- or p-orbital of Pd (111). This interaction induces an anti-bonding interaction between H and P in the hypophosphite ion, which is responsible for P-H cleavage. On the other hand, on Cu (111), the s-orbital of H and the s-orbital of P in a hypophosphite ion interact simultaneously with the p-orbital of Cu (111). This interaction barely induces an anti-bonding interaction between H and P in the hypophosphite ion. Such a difference in orbital interaction structures should be related to P-H cleavage activity and the reactivity difference of hypophosphite ion on each metal surface.

    元の言語English
    ジャーナルJournal of the Electrochemical Society
    158
    発行部数10
    DOI
    出版物ステータスPublished - 2011

    Fingerprint

    metal surfaces
    Density functional theory
    Metals
    Ions
    density functional theory
    orbitals
    ions
    interactions
    cleavage
    reactivity
    electroless deposition
    Electroless plating
    Reducing Agents
    Reducing agents
    Dehydrogenation
    dehydrogenation
    Electronic structure
    Chemical activation
    activation
    electronic structure

    ASJC Scopus subject areas

    • Electrochemistry
    • Electronic, Optical and Magnetic Materials
    • Materials Chemistry
    • Surfaces, Coatings and Films
    • Renewable Energy, Sustainability and the Environment
    • Condensed Matter Physics

    これを引用

    @article{42d1c0fbe2ee45e3ac737c9c73932d3e,
    title = "Density functional theory analysis for orbital interaction between hypophosphite ions and metal surfaces",
    abstract = "In order to elucidate the reactivity difference of hypophosphite ions used as reducing agents for electroless deposition on different metal surfaces, such as Pd and Cu, electronic structures of the activation states of hypophosphite ion oxidation on these surfaces were intensively analyzed by using Density Functional Theory (DFT). In the calculation, we focused on the dehydrogenation reaction which should be a rate-determining step in the elementary reaction steps. From the calculation results, a particular orbital interaction between the hypophosphite ion and the metal surface was observed. On Pd (111), the s-orbital of H in the hypophosphite ion interacts singly with the d- or p-orbital of Pd (111). This interaction induces an anti-bonding interaction between H and P in the hypophosphite ion, which is responsible for P-H cleavage. On the other hand, on Cu (111), the s-orbital of H and the s-orbital of P in a hypophosphite ion interact simultaneously with the p-orbital of Cu (111). This interaction barely induces an anti-bonding interaction between H and P in the hypophosphite ion. Such a difference in orbital interaction structures should be related to P-H cleavage activity and the reactivity difference of hypophosphite ion on each metal surface.",
    author = "Masahiro Kunimoto and Hiromi Nakai and Takayuki Homma",
    year = "2011",
    doi = "10.1149/1.3623782",
    language = "English",
    volume = "158",
    journal = "Journal of the Electrochemical Society",
    issn = "0013-4651",
    publisher = "Electrochemical Society, Inc.",
    number = "10",

    }

    TY - JOUR

    T1 - Density functional theory analysis for orbital interaction between hypophosphite ions and metal surfaces

    AU - Kunimoto, Masahiro

    AU - Nakai, Hiromi

    AU - Homma, Takayuki

    PY - 2011

    Y1 - 2011

    N2 - In order to elucidate the reactivity difference of hypophosphite ions used as reducing agents for electroless deposition on different metal surfaces, such as Pd and Cu, electronic structures of the activation states of hypophosphite ion oxidation on these surfaces were intensively analyzed by using Density Functional Theory (DFT). In the calculation, we focused on the dehydrogenation reaction which should be a rate-determining step in the elementary reaction steps. From the calculation results, a particular orbital interaction between the hypophosphite ion and the metal surface was observed. On Pd (111), the s-orbital of H in the hypophosphite ion interacts singly with the d- or p-orbital of Pd (111). This interaction induces an anti-bonding interaction between H and P in the hypophosphite ion, which is responsible for P-H cleavage. On the other hand, on Cu (111), the s-orbital of H and the s-orbital of P in a hypophosphite ion interact simultaneously with the p-orbital of Cu (111). This interaction barely induces an anti-bonding interaction between H and P in the hypophosphite ion. Such a difference in orbital interaction structures should be related to P-H cleavage activity and the reactivity difference of hypophosphite ion on each metal surface.

    AB - In order to elucidate the reactivity difference of hypophosphite ions used as reducing agents for electroless deposition on different metal surfaces, such as Pd and Cu, electronic structures of the activation states of hypophosphite ion oxidation on these surfaces were intensively analyzed by using Density Functional Theory (DFT). In the calculation, we focused on the dehydrogenation reaction which should be a rate-determining step in the elementary reaction steps. From the calculation results, a particular orbital interaction between the hypophosphite ion and the metal surface was observed. On Pd (111), the s-orbital of H in the hypophosphite ion interacts singly with the d- or p-orbital of Pd (111). This interaction induces an anti-bonding interaction between H and P in the hypophosphite ion, which is responsible for P-H cleavage. On the other hand, on Cu (111), the s-orbital of H and the s-orbital of P in a hypophosphite ion interact simultaneously with the p-orbital of Cu (111). This interaction barely induces an anti-bonding interaction between H and P in the hypophosphite ion. Such a difference in orbital interaction structures should be related to P-H cleavage activity and the reactivity difference of hypophosphite ion on each metal surface.

    UR - http://www.scopus.com/inward/record.url?scp=80052084445&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=80052084445&partnerID=8YFLogxK

    U2 - 10.1149/1.3623782

    DO - 10.1149/1.3623782

    M3 - Article

    AN - SCOPUS:80052084445

    VL - 158

    JO - Journal of the Electrochemical Society

    JF - Journal of the Electrochemical Society

    SN - 0013-4651

    IS - 10

    ER -