Covalent Bonding of CN to the Pt(111) Surface

W. Daum; F. Dederichs; J. E. Müller

doi:10.1103/PhysRevLett.80.766

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Covalent Bonding of CN to the Pt(111) Surface

W. Daum and F. Dederichs

J. E. Müller

Institut für Grenzflächenforschung und Vakuumphysik, Forschungszentrum Jülich, D-52425 Jülich, Germany

Institut für Schicht- und Ionentechnik, Forschungszentrum Jülich, D-52425 Jülich, Germany

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Phys. Rev. Lett. 80, 766 – Published 26 January, 1998Erratum Phys. Rev. Lett. 85, 2655 (2000)

DOI: https://doi.org/10.1103/PhysRevLett.80.766

Abstract

We present a vibrational study of the $CN / Pt (111)$ system immersed in acetonitrile, using optical sum-frequency generation. Frequencies of $2073 cm^{- 1}$ (on-top) and $1861 cm^{- 1}$ (hollow), distinctly above and below that of the isolated molecule, demonstrate a covalent CN-metal bond. Cluster calculations show that the strengthening and weakening of the C-N bond at the on-top and hollow sites is due to a surface-induced depletion of the antibonding $4 σ$ and bonding $1 π$ orbitals, respectively. We illustrate our results with a comparison to the reference $CO / Pt (111)$ system.

Erratum

Erratum: Covalent Bonding of CN to the Pt(111) Surface [Phys. Rev. Lett. 80, 766 (1998)]

W. Daum, F. Dederichs, and J. E. Müller

Phys. Rev. Lett. 85, 2655 (2000)

References (15)

K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds (Wiley, New York, 1986).
K. A. Friedrich, W. Daum, C. Klünker, D. Knabben, U. Stimming, and H. Ibach, Surf. Sci. 335, 315 (1995), and references therein.
P. S. Bagus, C. J. Nelin, W. Müller, M. R. Philpott, and H. Seki, Phys. Rev. Lett. 58, 559 (1987).
C. J. Nelin, P. S. Bagus, and M. R. Philpott, J. Chem. Phys. 87, 2170 (1987).
J. E. Müller, R. O. Jones, and J. Harris, J. Chem. Phys. 79, 1874 (1983).
F. Dederichs and W. Daum (to be published).
F. Kitamura, M. Takahashi, and M. Ito, Surf. Sci. 223, 493 (1989).
S.-C. Chang, X. Jiang, J. D. Roth, and M. J. Weaver, J. Phys. Chem. 95, 5378 (1991).
G. Herzberg, Spectra of Diatomic Molecules (Van Nostrand Reinhold, New York, 1950).
H. Yang, T. C. Caves, and J. L. Whitten, J. Chem. Phys. 103, 8756 (1995).
For $CO / Pt (111)$ is acetonitrile without externally applied potential we find an on-top frequency of $2075 cm^{- 1}$ , about $20 cm^{- 1}$ lower than for the $Pt / vacuum$ interface.
M. Tüshaus, E. Schweizer, P. Hollins, and A. M. Bradshaw, J. Electron Spectrosc. Relat. Phenom. 44, 305 (1987).
A positive $5 σ$ energy does not contradict the stability of isolated ${CN}^{-}$ . The electron affinity of CN (3.8 eV) is the average of the $5 σ$ energies with occupations 1 and 2.
J. P. Flament and M. Tadjeddine, Chem. Phys. Lett. 238, 193 (1995).
R. S. Mulliken, J. Chem. Phys. 23, 1833 (1955); see also J. E. Müller, Surf. Sci. 178, 589 (1986).

[c1] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds (Wiley, New York, 1986).

[c2] K. A. Friedrich, W. Daum, C. Klünker, D. Knabben, U. Stimming, and H. Ibach, Surf. Sci. 335, 315 (1995), and references therein.

[c3] P. S. Bagus, C. J. Nelin, W. Müller, M. R. Philpott, and H. Seki, Phys. Rev. Lett. 58, 559 (1987).

[c4] C. J. Nelin, P. S. Bagus, and M. R. Philpott, J. Chem. Phys. 87, 2170 (1987).

[c5] J. E. Müller, R. O. Jones, and J. Harris, J. Chem. Phys. 79, 1874 (1983).

[c6] F. Dederichs and W. Daum (to be published).

[c7] F. Kitamura, M. Takahashi, and M. Ito, Surf. Sci. 223, 493 (1989).

[c8] S.-C. Chang, X. Jiang, J. D. Roth, and M. J. Weaver, J. Phys. Chem. 95, 5378 (1991).

[c9] G. Herzberg, Spectra of Diatomic Molecules (Van Nostrand Reinhold, New York, 1950).

[c10] H. Yang, T. C. Caves, and J. L. Whitten, J. Chem. Phys. 103, 8756 (1995).

[c11] For $CO / Pt (111)$ is acetonitrile without externally applied potential we find an on-top frequency of $2075 cm^{- 1}$ , about $20 cm^{- 1}$ lower than for the $Pt / vacuum$ interface.

[c12] M. Tüshaus, E. Schweizer, P. Hollins, and A. M. Bradshaw, J. Electron Spectrosc. Relat. Phenom. 44, 305 (1987).

[c13] A positive $5 σ$ energy does not contradict the stability of isolated ${CN}^{-}$ . The electron affinity of CN (3.8 eV) is the average of the $5 σ$ energies with occupations 1 and 2.

[c14] J. P. Flament and M. Tadjeddine, Chem. Phys. Lett. 238, 193 (1995).

[c15] R. S. Mulliken, J. Chem. Phys. 23, 1833 (1955); see also J. E. Müller, Surf. Sci. 178, 589 (1986).

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Covalent Bonding of CN to the Pt(111) Surface

Abstract

Erratum

Erratum: Covalent Bonding of CN to the Pt(111) Surface [Phys. Rev. Lett. 80, 766 (1998)]

References (15)

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