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Issue 41, 2009
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On the chemical bonding effects in the Raman response: Benzenethiol adsorbed on silver clusters

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Abstract

We study the effects of chemical bonding on Raman scattering from benzenethiol chemisorbed on silver clusters using time-dependent density functional theory (TDDFT). Raman scattering cross sections are computed using a formalism that employs analytical derivatives of frequency-dependent electronic polarizabilities, which treats both off-resonant and resonant enhancement within the same scheme. In the off-resonant regime, Raman scattering into molecular vibrational modes is enhanced by one order of magnitude and shows pronounced dependence on the orientation and the local symmetry of the molecule. Additional strong enhancement of the order of 102 arises from resonant transitions to mixed metal–molecular electronic states. The Raman enhancement is analyzed using Raman excitation profiles (REPs) for the range of excitation energies 1.6–3.0 eV, in which isolated benzenethiol does not have electronic transitions. The computed vibrational frequency shifts and relative Raman scattering cross sections of the metal–molecular complexes are in good agreement with experimental data on surface enhanced Raman scattering (SERS) from benzenethiol adsorbed on silver surfaces. Characterization and understanding of these effects, associated with chemical enhancement mechanism, may be used to improve the detection sensitivity in molecular Raman scattering.

Graphical abstract: On the chemical bonding effects in the Raman response: Benzenethiol adsorbed on silver clusters

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Publication details

The article was received on 06 Apr 2009, accepted on 06 Aug 2009 and first published on 26 Aug 2009


Article type: Paper
DOI: 10.1039/B906885F
Citation: Phys. Chem. Chem. Phys., 2009,11, 9401-9411
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    On the chemical bonding effects in the Raman response: Benzenethiol adsorbed on silver clusters

    S. K. Saikin, R. Olivares-Amaya, D. Rappoport, M. Stopa and A. Aspuru-Guzik, Phys. Chem. Chem. Phys., 2009, 11, 9401
    DOI: 10.1039/B906885F

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