DOI: 10.1063/1.455324. A theoretical study of methyl chemisorption on Ni(111)

A theoretical study of methyl chemisorption on Ni(111)

10.1063/1.455324

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Calculations including electron correlation have been performed for methyl adsorbed on nickel clusters mimicking the Ni(111) surface. The chemisorption energies are evaluated following a recently developed scheme, in which the cluster is prepared for bonding. In this way cluster dependent oscillations of the chemisorption energies are largely eliminated. By also using calculated vibrational frequencies of the adsorbed methyl an almost certain assignment of the preferred chemisorption site is obtained. Methyl is found to adsorb in the threefold hollow site with a chemisorption energy in the range 50–55 kcal/mol. The origin of the soft C–H frequencies observed experimentally is a charge transfer from the metal into the C–H antibonding orbitals. The only weak sign of a direct metal–carbon–hydrogen interaction in the calculations is that the C–H frequency is slightly lower for an eclipsed compared to a staggered orientation of methyl in the threefold hollow. The present results are compared to previous experimental and theoretical results for methyl adsorbed on metal surfaces.

Bibliography

SchÃ¼le, J., Siegbahn, P., & Wahlgren, U. (1988). A theoretical study of methyl chemisorption on Ni(111). The Journal of Chemical Physics, 89(11), 6982â6988.

Authors 3

Josef Schüle (first)
Per Siegbahn (additional)
Ulf Wahlgren (additional)

References 35 Referenced 88

10.1021/ja00266a042 / J. Am. Chem. Soc. (1986)
10.1063/1.451211 / J. Chem. Phys. (1986)
{'key': '2024021006544993200_r2a'}
10.1063/1.453060 / J. Chem. Phys. (1987)
10.1103/PhysRevLett.40.1044 / Phys. Rev. Lett. (1978)
10.1021/j150669a031 / J. Phys. Chem. (1984)
10.1073/pnas.78.7.3981 / Proc. Natl. Acad. Sci. U.S.A. (1981)
{'key': '2024021006544993200_r6', 'first-page': '441', 'volume': '127', 'year': '1982', 'journal-title': 'Surf. Sci.'} / Surf. Sci. (1982)
10.1021/ja00211a015 / J. Am. Chem. Soc. (1988)
{'key': '2024021006544993200_r8', 'first-page': 'L863', 'volume': '176', 'year': '1986', 'journal-title': 'Surf. Sci.'} / Surf. Sci. (1986)
10.1116/1.571423 / J. Vac. Sci. Technol. (1982)
10.1016/0009-2614(88)85024-3 / Chem. Phys. Lett. (1988)
10.1016/0301-0104(87)85101-7 / Chem. Phys. (1987)
10.1063/1.438240 / J. Chem. Phys. (1979)
10.1063/1.1673095 / J. Chem. Phys. (1970)
10.1063/1.433731 / J. Chem. Phys. (1977)
10.1007/BF00527141 / Theor. Chim. Acta (1988)
{'key': '2024021006544993200_r16'}
10.1063/1.1696113 / J. Chem. Phys. (1965)
10.1016/0301-0104(80)80045-0 / Chem. Phys. (1980)
10.1002/qua.560230602 / Intern. J. Quantum Chem. (1983)
{'key': '2024021006544993200_r20'}
10.1063/1.441645 / J. Chem. Phys. (1981)
10.1016/0009-2614(85)85380-X / Chem. Phys. Lett. (1985)
10.1063/1.449704 / J. Chem. Phys. (1985)
10.1063/1.435626 / J. Chem. Phys. (1978)
{'key': '2024021006544993200_r25'}
10.1080/10408438108243637 / CRC Crit. Rev. Solid State Mat. Sci. (1981)
10.1016/0167-5729(86)90003-8 / Surf. Sci. Rep. (1986)
10.1063/1.1680935 / J. Chem. Phys. (1974)
10.1103/PhysRevLett.54.1551 / Phys. Rev. Lett. (1985)
10.1016/0009-2614(82)83386-1 / Chem. Phys. Lett. (1982)
10.1063/1.1701708 / J. Chem. Phys. (1967)
10.1021/ja00396a054 / J. Am. Chem. Soc. (1981)
10.1021/j100322a015 / J. Phys. Chem. (1988)

Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 9:10 a.m.)
Deposited	1 year, 6 months ago (Feb. 10, 2024, 3:47 a.m.)
Indexed	3 weeks, 1 day ago (Aug. 7, 2025, 5:05 p.m.)
Issued	36 years, 8 months ago (Dec. 1, 1988)
Published	36 years, 8 months ago (Dec. 1, 1988)
Published Print	36 years, 8 months ago (Dec. 1, 1988)

Funders 0

None

BibTeX

@article{Sch_le_1988, title={A theoretical study of methyl chemisorption on Ni(111)}, volume={89}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.455324}, DOI={10.1063/1.455324}, number={11}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Schüle, Josef and Siegbahn, Per and Wahlgren, Ulf}, year={1988}, month=dec, pages={6982–6988} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        8,
        7
      ]
    ],
    "date-time": "2025-08-07T21:05:16Z",
    "timestamp": 1754600716327
  },
  "reference-count": 35,
  "publisher": "AIP Publishing",
  "issue": "11",
  "content-domain": {
    "domain": [
      "pubs.aip.org"
    ],
    "crossmark-restriction": true
  },
  "published-print": {
    "date-parts": [
      [
        1988,
        12,
        1
      ]
    ]
  },
  "abstract": "<jats:p>Calculations including electron correlation have been performed for methyl adsorbed on nickel clusters mimicking the Ni(111) surface. The chemisorption energies are evaluated following a recently developed scheme, in which the cluster is prepared for bonding. In this way cluster dependent oscillations of the chemisorption energies are largely eliminated. By also using calculated vibrational frequencies of the adsorbed methyl an almost certain assignment of the preferred chemisorption site is obtained. Methyl is found to adsorb in the threefold hollow site with a chemisorption energy in the range 50\u201355 kcal/mol. The origin of the soft C\u2013H frequencies observed experimentally is a charge transfer from the metal into the C\u2013H antibonding orbitals. The only weak sign of a direct metal\u2013carbon\u2013hydrogen interaction in the calculations is that the C\u2013H frequency is slightly lower for an eclipsed compared to a staggered orientation of methyl in the threefold hollow. The present results are compared to previous experimental and theoretical results for methyl adsorbed on metal surfaces.</jats:p>",
  "DOI": "10.1063/1.455324",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2002,
        7,
        26
      ]
    ],
    "date-time": "2002-07-26T13:10:26Z",
    "timestamp": 1027689026000
  },
  "page": "6982-6988",
  "update-policy": "http://dx.doi.org/10.1063/aip-crossmark-policy-page",
  "source": "Crossref",
  "is-referenced-by-count": 88,
  "title": "A theoretical study of methyl chemisorption on Ni(111)",
  "prefix": "10.1063",
  "volume": "89",
  "author": [
    {
      "given": "Josef",
      "family": "Sch\u00fcle",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Institute of Theoretical Physics, University of Stockholm, Vanadisv\u00e4gen 9, S-11346 Stockholm, Sweden"
        }
      ]
    },
    {
      "given": "Per",
      "family": "Siegbahn",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Institute of Theoretical Physics, University of Stockholm, Vanadisv\u00e4gen 9, S-11346 Stockholm, Sweden"
        }
      ]
    },
    {
      "given": "Ulf",
      "family": "Wahlgren",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Institute of Theoretical Physics, University of Stockholm, Vanadisv\u00e4gen 9, S-11346 Stockholm, Sweden"
        }
      ]
    }
  ],
  "member": "317",
  "reference": [
    {
      "key": "2024021006544993200_r1",
      "doi-asserted-by": "crossref",
      "first-page": "1315",
      "DOI": "10.1021/ja00266a042",
      "volume": "108",
      "year": "1986",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021006544993200_r2",
      "doi-asserted-by": "crossref",
      "first-page": "1693",
      "DOI": "10.1063/1.451211",
      "volume": "85",
      "year": "1986",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r2a"
    },
    {
      "key": "2024021006544993200_r2b",
      "doi-asserted-by": "crossref",
      "first-page": "2724",
      "DOI": "10.1063/1.453060",
      "volume": "87",
      "year": "1987",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r3",
      "doi-asserted-by": "crossref",
      "first-page": "1044",
      "DOI": "10.1103/PhysRevLett.40.1044",
      "volume": "40",
      "year": "1978",
      "journal-title": "Phys. Rev. Lett."
    },
    {
      "key": "2024021006544993200_r4",
      "doi-asserted-by": "crossref",
      "first-page": "6209",
      "DOI": "10.1021/j150669a031",
      "volume": "88",
      "year": "1984",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021006544993200_r5",
      "doi-asserted-by": "crossref",
      "first-page": "3981",
      "DOI": "10.1073/pnas.78.7.3981",
      "volume": "78",
      "year": "1981",
      "journal-title": "Proc. Natl. Acad. Sci. U.S.A."
    },
    {
      "key": "2024021006544993200_r6",
      "first-page": "441",
      "volume": "127",
      "year": "1982",
      "journal-title": "Surf. Sci."
    },
    {
      "key": "2024021006544993200_r7",
      "doi-asserted-by": "crossref",
      "first-page": "749",
      "DOI": "10.1021/ja00211a015",
      "volume": "110",
      "year": "1988",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021006544993200_r8",
      "first-page": "L863",
      "volume": "176",
      "year": "1986",
      "journal-title": "Surf. Sci."
    },
    {
      "key": "2024021006544993200_r9",
      "doi-asserted-by": "crossref",
      "first-page": "527",
      "DOI": "10.1116/1.571423",
      "volume": "20",
      "year": "1982",
      "journal-title": "J. Vac. Sci. Technol."
    },
    {
      "key": "2024021006544993200_r10",
      "doi-asserted-by": "crossref",
      "first-page": "265",
      "DOI": "10.1016/0009-2614(88)85024-3",
      "volume": "149",
      "year": "1988",
      "journal-title": "Chem. Phys. Lett."
    },
    {
      "key": "2024021006544993200_r11",
      "doi-asserted-by": "crossref",
      "first-page": "325",
      "DOI": "10.1016/0301-0104(87)85101-7",
      "volume": "112",
      "year": "1987",
      "journal-title": "Chem. Phys."
    },
    {
      "key": "2024021006544993200_r12",
      "doi-asserted-by": "crossref",
      "first-page": "4339",
      "DOI": "10.1063/1.438240",
      "volume": "71",
      "year": "1979",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r13",
      "doi-asserted-by": "crossref",
      "first-page": "1033",
      "DOI": "10.1063/1.1673095",
      "volume": "52",
      "year": "1970",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r14",
      "doi-asserted-by": "crossref",
      "first-page": "4377",
      "DOI": "10.1063/1.433731",
      "volume": "66",
      "year": "1977",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r15",
      "doi-asserted-by": "crossref",
      "first-page": "167",
      "DOI": "10.1007/BF00527141",
      "volume": "74",
      "year": "1988",
      "journal-title": "Theor. Chim. Acta"
    },
    {
      "key": "2024021006544993200_r16"
    },
    {
      "key": "2024021006544993200_r17",
      "doi-asserted-by": "crossref",
      "first-page": "1293",
      "DOI": "10.1063/1.1696113",
      "volume": "42",
      "year": "1965",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r18",
      "doi-asserted-by": "crossref",
      "first-page": "157",
      "DOI": "10.1016/0301-0104(80)80045-0",
      "volume": "48",
      "year": "1980",
      "journal-title": "Chem. Phys."
    },
    {
      "key": "2024021006544993200_r19",
      "doi-asserted-by": "crossref",
      "first-page": "1869",
      "DOI": "10.1002/qua.560230602",
      "volume": "23",
      "year": "1983",
      "journal-title": "Intern. J. Quantum Chem."
    },
    {
      "key": "2024021006544993200_r20"
    },
    {
      "key": "2024021006544993200_r21",
      "doi-asserted-by": "crossref",
      "first-page": "4566",
      "DOI": "10.1063/1.441645",
      "volume": "74",
      "year": "1981",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r22",
      "doi-asserted-by": "crossref",
      "first-page": "515",
      "DOI": "10.1016/0009-2614(85)85380-X",
      "volume": "119",
      "year": "1985",
      "journal-title": "Chem. Phys. Lett."
    },
    {
      "key": "2024021006544993200_r23",
      "doi-asserted-by": "crossref",
      "first-page": "5351",
      "DOI": "10.1063/1.449704",
      "volume": "83",
      "year": "1985",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r24",
      "doi-asserted-by": "crossref",
      "first-page": "5077",
      "DOI": "10.1063/1.435626",
      "volume": "68",
      "year": "1978",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r25"
    },
    {
      "key": "2024021006544993200_r26",
      "doi-asserted-by": "crossref",
      "first-page": "261",
      "DOI": "10.1080/10408438108243637",
      "volume": "10",
      "year": "1981",
      "journal-title": "CRC Crit. Rev. Solid State Mat. Sci."
    },
    {
      "key": "2024021006544993200_r27",
      "doi-asserted-by": "crossref",
      "first-page": "1",
      "DOI": "10.1016/0167-5729(86)90003-8",
      "volume": "6",
      "year": "1986",
      "journal-title": "Surf. Sci. Rep."
    },
    {
      "key": "2024021006544993200_r28",
      "doi-asserted-by": "crossref",
      "first-page": "4528",
      "DOI": "10.1063/1.1680935",
      "volume": "60",
      "year": "1974",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r29",
      "doi-asserted-by": "crossref",
      "first-page": "1551",
      "DOI": "10.1103/PhysRevLett.54.1551",
      "volume": "54",
      "year": "1985",
      "journal-title": "Phys. Rev. Lett."
    },
    {
      "key": "2024021006544993200_r30",
      "doi-asserted-by": "crossref",
      "first-page": "120",
      "DOI": "10.1016/0009-2614(82)83386-1",
      "volume": "89",
      "year": "1982",
      "journal-title": "Chem. Phys. Lett."
    },
    {
      "key": "2024021006544993200_r31",
      "doi-asserted-by": "crossref",
      "first-page": "4834",
      "DOI": "10.1063/1.1701708",
      "volume": "47",
      "year": "1967",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021006544993200_r32",
      "doi-asserted-by": "crossref",
      "first-page": "1574",
      "DOI": "10.1021/ja00396a054",
      "volume": "103",
      "year": "1981",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021006544993200_r33",
      "doi-asserted-by": "crossref",
      "first-page": "3079",
      "DOI": "10.1021/j100322a015",
      "volume": "92",
      "year": "1988",
      "journal-title": "J. Phys. Chem."
    }
  ],
  "container-title": "The Journal of Chemical Physics",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/89/11/6982/18973489/6982_1_online.pdf",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "syndication"
    },
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/89/11/6982/18973489/6982_1_online.pdf",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2024,
        2,
        10
      ]
    ],
    "date-time": "2024-02-10T08:47:07Z",
    "timestamp": 1707554827000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://pubs.aip.org/jcp/article/89/11/6982/314506/A-theoretical-study-of-methyl-chemisorption-on-Ni"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1988,
        12,
        1
      ]
    ]
  },
  "references-count": 35,
  "journal-issue": {
    "issue": "11",
    "published-print": {
      "date-parts": [
        [
          1988,
          12,
          1
        ]
      ]
    }
  },
  "URL": "http://dx.doi.org/10.1063/1.455324",
  "relation": {},
  "ISSN": [
    "0021-9606",
    "1089-7690"
  ],
  "subject": [],
  "published-other": {
    "date-parts": [
      [
        1988,
        12,
        1
      ]
    ]
  },
  "published": {
    "date-parts": [
      [
        1988,
        12,
        1
      ]
    ]
  }
}