DFT calculation analysis of the infrared spectra of ethylene adsorbed on Cu(110), Pd(110), and Ag(110)

Koichi Itoh, Tairiku Kiyohara, Hironao Shinohara, Chikaomi Ohe, Yoshiumi Kawamura, Hiromi Nakai

    Research output: Contribution to journalArticle

    29 Citations (Scopus)

    Abstract

    A density functional theory (DFT) calculation was performed on the cluster models of ethylene on Cu(110), Ag(110), and Pd(110) to clarify the correlation between the IR spectra of the adsorbate and the modes of ethylene-surface interaction. The metal surfaces were modeled by two- or three-layered clusters consisting of 13-34 metal atoms. Four kinds of adsorption sites were considered: atop bonding sites with the CC bond parallel and perpendicular to the <11̄0> direction (ST and LT sites), a short bridge site with the CC bond parallel to the <11̄0> direction (SB site), and a long bridge site with the CC bond perpendicular to the <11̄0> direction (LB site). The results of calculations for three-layered models consisting of more than 20 metals could be compared reasonably with the experimental data. The comparison indicated that (i) upon increasing surface coverage, ethylene on Cu(110) converts its adsorption site from an SB to an ST site, (ii) ethylene adsorbs at an LT site of Ag(110), and (iii) ethylene on Pd(110) takes on an ST site. These conclusions are consistent with those derived from STM and other spectroscopic measurements including UPS and NEXAFS, indicating that the DFT calculation on the cluster models is efficient for the analysis of the IR spectra of ethylene adsorbed on metal surfaces, which delineates the adsorption modes. The contribution of donation and back-donation of electrons to the ethylene-metal bonding was estimated by calculating the projections to the π-bonding and π*-antibonding orbitals of the isolated ethylene in the adsorbed geometries. The results proved that both the π donation and π* back-donation make appreciable contributions to the ethylene-surface interaction on Cu(110), whereas the π* back-donation is negligible in the ethylene-Ag(110) interaction. It was suggested that the frequency increase of the CH2 out-of-plane wagging vibration from that of the free ethylene observed for ethylene on Ag(110) is a measure of the contribution of the π donation to the ethylene-surface interaction.

    Original languageEnglish
    Pages (from-to)10714-10721
    Number of pages8
    JournalJournal of Physical Chemistry B
    Volume106
    Issue number41
    DOIs
    Publication statusPublished - 2002 Oct 17

    Fingerprint

    Density functional theory
    Ethylene
    ethylene
    infrared spectra
    density functional theory
    Infrared radiation
    Metals
    surface reactions
    Adsorption
    adsorption
    metal surfaces
    metal bonding
    Adsorbates
    metals
    projection
    orbitals
    Atoms
    vibration
    Geometry
    Electrons

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry

    Cite this

    DFT calculation analysis of the infrared spectra of ethylene adsorbed on Cu(110), Pd(110), and Ag(110). / Itoh, Koichi; Kiyohara, Tairiku; Shinohara, Hironao; Ohe, Chikaomi; Kawamura, Yoshiumi; Nakai, Hiromi.

    In: Journal of Physical Chemistry B, Vol. 106, No. 41, 17.10.2002, p. 10714-10721.

    Research output: Contribution to journalArticle

    Itoh, Koichi ; Kiyohara, Tairiku ; Shinohara, Hironao ; Ohe, Chikaomi ; Kawamura, Yoshiumi ; Nakai, Hiromi. / DFT calculation analysis of the infrared spectra of ethylene adsorbed on Cu(110), Pd(110), and Ag(110). In: Journal of Physical Chemistry B. 2002 ; Vol. 106, No. 41. pp. 10714-10721.
    @article{e3fe4192a91c4400a52fedd5839b8b42,
    title = "DFT calculation analysis of the infrared spectra of ethylene adsorbed on Cu(110), Pd(110), and Ag(110)",
    abstract = "A density functional theory (DFT) calculation was performed on the cluster models of ethylene on Cu(110), Ag(110), and Pd(110) to clarify the correlation between the IR spectra of the adsorbate and the modes of ethylene-surface interaction. The metal surfaces were modeled by two- or three-layered clusters consisting of 13-34 metal atoms. Four kinds of adsorption sites were considered: atop bonding sites with the CC bond parallel and perpendicular to the <11̄0> direction (ST and LT sites), a short bridge site with the CC bond parallel to the <11̄0> direction (SB site), and a long bridge site with the CC bond perpendicular to the <11̄0> direction (LB site). The results of calculations for three-layered models consisting of more than 20 metals could be compared reasonably with the experimental data. The comparison indicated that (i) upon increasing surface coverage, ethylene on Cu(110) converts its adsorption site from an SB to an ST site, (ii) ethylene adsorbs at an LT site of Ag(110), and (iii) ethylene on Pd(110) takes on an ST site. These conclusions are consistent with those derived from STM and other spectroscopic measurements including UPS and NEXAFS, indicating that the DFT calculation on the cluster models is efficient for the analysis of the IR spectra of ethylene adsorbed on metal surfaces, which delineates the adsorption modes. The contribution of donation and back-donation of electrons to the ethylene-metal bonding was estimated by calculating the projections to the π-bonding and π*-antibonding orbitals of the isolated ethylene in the adsorbed geometries. The results proved that both the π donation and π* back-donation make appreciable contributions to the ethylene-surface interaction on Cu(110), whereas the π* back-donation is negligible in the ethylene-Ag(110) interaction. It was suggested that the frequency increase of the CH2 out-of-plane wagging vibration from that of the free ethylene observed for ethylene on Ag(110) is a measure of the contribution of the π donation to the ethylene-surface interaction.",
    author = "Koichi Itoh and Tairiku Kiyohara and Hironao Shinohara and Chikaomi Ohe and Yoshiumi Kawamura and Hiromi Nakai",
    year = "2002",
    month = "10",
    day = "17",
    doi = "10.1021/jp021377p",
    language = "English",
    volume = "106",
    pages = "10714--10721",
    journal = "Journal of Physical Chemistry B Materials",
    issn = "1520-6106",
    publisher = "American Chemical Society",
    number = "41",

    }

    TY - JOUR

    T1 - DFT calculation analysis of the infrared spectra of ethylene adsorbed on Cu(110), Pd(110), and Ag(110)

    AU - Itoh, Koichi

    AU - Kiyohara, Tairiku

    AU - Shinohara, Hironao

    AU - Ohe, Chikaomi

    AU - Kawamura, Yoshiumi

    AU - Nakai, Hiromi

    PY - 2002/10/17

    Y1 - 2002/10/17

    N2 - A density functional theory (DFT) calculation was performed on the cluster models of ethylene on Cu(110), Ag(110), and Pd(110) to clarify the correlation between the IR spectra of the adsorbate and the modes of ethylene-surface interaction. The metal surfaces were modeled by two- or three-layered clusters consisting of 13-34 metal atoms. Four kinds of adsorption sites were considered: atop bonding sites with the CC bond parallel and perpendicular to the <11̄0> direction (ST and LT sites), a short bridge site with the CC bond parallel to the <11̄0> direction (SB site), and a long bridge site with the CC bond perpendicular to the <11̄0> direction (LB site). The results of calculations for three-layered models consisting of more than 20 metals could be compared reasonably with the experimental data. The comparison indicated that (i) upon increasing surface coverage, ethylene on Cu(110) converts its adsorption site from an SB to an ST site, (ii) ethylene adsorbs at an LT site of Ag(110), and (iii) ethylene on Pd(110) takes on an ST site. These conclusions are consistent with those derived from STM and other spectroscopic measurements including UPS and NEXAFS, indicating that the DFT calculation on the cluster models is efficient for the analysis of the IR spectra of ethylene adsorbed on metal surfaces, which delineates the adsorption modes. The contribution of donation and back-donation of electrons to the ethylene-metal bonding was estimated by calculating the projections to the π-bonding and π*-antibonding orbitals of the isolated ethylene in the adsorbed geometries. The results proved that both the π donation and π* back-donation make appreciable contributions to the ethylene-surface interaction on Cu(110), whereas the π* back-donation is negligible in the ethylene-Ag(110) interaction. It was suggested that the frequency increase of the CH2 out-of-plane wagging vibration from that of the free ethylene observed for ethylene on Ag(110) is a measure of the contribution of the π donation to the ethylene-surface interaction.

    AB - A density functional theory (DFT) calculation was performed on the cluster models of ethylene on Cu(110), Ag(110), and Pd(110) to clarify the correlation between the IR spectra of the adsorbate and the modes of ethylene-surface interaction. The metal surfaces were modeled by two- or three-layered clusters consisting of 13-34 metal atoms. Four kinds of adsorption sites were considered: atop bonding sites with the CC bond parallel and perpendicular to the <11̄0> direction (ST and LT sites), a short bridge site with the CC bond parallel to the <11̄0> direction (SB site), and a long bridge site with the CC bond perpendicular to the <11̄0> direction (LB site). The results of calculations for three-layered models consisting of more than 20 metals could be compared reasonably with the experimental data. The comparison indicated that (i) upon increasing surface coverage, ethylene on Cu(110) converts its adsorption site from an SB to an ST site, (ii) ethylene adsorbs at an LT site of Ag(110), and (iii) ethylene on Pd(110) takes on an ST site. These conclusions are consistent with those derived from STM and other spectroscopic measurements including UPS and NEXAFS, indicating that the DFT calculation on the cluster models is efficient for the analysis of the IR spectra of ethylene adsorbed on metal surfaces, which delineates the adsorption modes. The contribution of donation and back-donation of electrons to the ethylene-metal bonding was estimated by calculating the projections to the π-bonding and π*-antibonding orbitals of the isolated ethylene in the adsorbed geometries. The results proved that both the π donation and π* back-donation make appreciable contributions to the ethylene-surface interaction on Cu(110), whereas the π* back-donation is negligible in the ethylene-Ag(110) interaction. It was suggested that the frequency increase of the CH2 out-of-plane wagging vibration from that of the free ethylene observed for ethylene on Ag(110) is a measure of the contribution of the π donation to the ethylene-surface interaction.

    UR - http://www.scopus.com/inward/record.url?scp=0037126121&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=0037126121&partnerID=8YFLogxK

    U2 - 10.1021/jp021377p

    DO - 10.1021/jp021377p

    M3 - Article

    AN - SCOPUS:0037126121

    VL - 106

    SP - 10714

    EP - 10721

    JO - Journal of Physical Chemistry B Materials

    JF - Journal of Physical Chemistry B Materials

    SN - 1520-6106

    IS - 41

    ER -