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The modes observed in any spectroscopic experiment are dictated by the symmetry of the molecules and are usually summarized by selection rules. When molecules are adsorbed to a surface, the symmetry of the system can change, slightly modifying the symmetry of the molecule, which can lead to differences in mode selection. One common way in which selection rules are modified arises from the fact that many molecules that have a center of symmetry lose that feature when adsorbed to a surface.

The loss of a center of symmetry eliminates the requirements of the mutual exclusion rule , which dictates that modes can only be either Raman or Infrared active. Thus modes that would normally appear only in the infrared spectrum of the free molecule can appear in the SERS spectrum. A molecule's symmetry can be changed in different ways depending on the orientation in which the molecule is attached to the surface. In some experiments, it is possible to determine the orientation of adsorption to the surface from the SERS spectrum, as different modes will be present depending on how the symmetry is modified.

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Surface-Enhanced Raman Scattering - Physics and Applications | Katrin Kneipp | Springer

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