Electronic mechanism of the surface enhanced Raman scattering

Hiromi Nakai; Hiroshi Nakatsuji

doi:10.1063/1.469704

Electronic mechanism of the surface enhanced Raman scattering

Hiromi Nakai^*, Hiroshi Nakatsuji

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

36 Citations (Scopus)

Abstract

Electronic mechanism of the surface enhanced Raman scattering (SERS) is investigated by an ab initio molecular orbital theory. The time-dependent Hartree-Fock method is used to calculate the polarizability of the surface-molecule interacting system. For representing the surface effect, we use small solid clusters Ag₂, Ag₁₀, K₂, Pd ₂, and MgO. The present method succeeds in describing the enhancement of the Raman intensity for the adsorbed CO molecule. The maximum intensity of the Ag₁₀CO system is calculated to be seven orders of magnitude larger than that of the free CO molecule. Furthermore, the wavelength dependence of the Raman intensity calculated by the Ag₁₀CO system agrees with the experimental spectrum. The electronic mechanism of the SERS is due to the resonance transitions, in which the surface polarization and the surface-molecule interaction are very important. This mechanism explains the orientation- and distance-dependencies in the surface-adsorbate interacting systems.

Original language	English
Pages (from-to)	2286-2294
Number of pages	9
Journal	The Journal of Chemical Physics
Volume	103
Issue number	6
DOIs	https://doi.org/10.1063/1.469704
Publication status	Published - 1995
Externally published	Yes

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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abstract = "Electronic mechanism of the surface enhanced Raman scattering (SERS) is investigated by an ab initio molecular orbital theory. The time-dependent Hartree-Fock method is used to calculate the polarizability of the surface-molecule interacting system. For representing the surface effect, we use small solid clusters Ag2, Ag10, K2, Pd 2, and MgO. The present method succeeds in describing the enhancement of the Raman intensity for the adsorbed CO molecule. The maximum intensity of the Ag10CO system is calculated to be seven orders of magnitude larger than that of the free CO molecule. Furthermore, the wavelength dependence of the Raman intensity calculated by the Ag10CO system agrees with the experimental spectrum. The electronic mechanism of the SERS is due to the resonance transitions, in which the surface polarization and the surface-molecule interaction are very important. This mechanism explains the orientation- and distance-dependencies in the surface-adsorbate interacting systems.",

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AU - Nakai, Hiromi

AU - Nakatsuji, Hiroshi

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AB - Electronic mechanism of the surface enhanced Raman scattering (SERS) is investigated by an ab initio molecular orbital theory. The time-dependent Hartree-Fock method is used to calculate the polarizability of the surface-molecule interacting system. For representing the surface effect, we use small solid clusters Ag2, Ag10, K2, Pd 2, and MgO. The present method succeeds in describing the enhancement of the Raman intensity for the adsorbed CO molecule. The maximum intensity of the Ag10CO system is calculated to be seven orders of magnitude larger than that of the free CO molecule. Furthermore, the wavelength dependence of the Raman intensity calculated by the Ag10CO system agrees with the experimental spectrum. The electronic mechanism of the SERS is due to the resonance transitions, in which the surface polarization and the surface-molecule interaction are very important. This mechanism explains the orientation- and distance-dependencies in the surface-adsorbate interacting systems.

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Electronic mechanism of the surface enhanced Raman scattering

Abstract

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