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

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

2009-09-04

arxiv.org/abs/0909.0951v1

Physics

Condensed Matter

Mesoscale and Nanoscale Physics

25 pages, 14 figures. Phys. Chem. Chem. Phys. in press

Scientific paper

10.1039/b906885f

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 $10^2$ 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) for 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.

Affiliated with

Also associated with

No associations

Rating

On the chemical bonding effects in the Raman response: Benzenethiol adsorbed on silver clusters does not yet have a rating. At this time, there are no reviews or comments for this scientific paper.

If you have personal experience with On the chemical bonding effects in the Raman response: Benzenethiol adsorbed on silver clusters, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and On the chemical bonding effects in the Raman response: Benzenethiol adsorbed on silver clusters will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFWR-SCP-O-160781