Resonance Raman Vibrational Mode Enhancement of Adsorbed Benzenethiols on CdSe Is Predominantly Franck-Condon in Nature and Governed by Symmetry.

Here, we report mode-specific resonance Raman enhancements of ligands covalently bound to the surface of colloidal CdSe nanocrystals (NCs). By the systematic comparison of a set of structural derivatives, the extent of resonance Raman enhancement is shown to be directly related to the molecular symmetry of the bound ligands. The enhancement dependence on molecular symmetry is further discussed in terms of Franck-Condon and Herzberg-Teller contributions and their associated selection rules. We further show that resonance Raman may be used to distinguish between possible surface binding motifs of bidentate ligands under continuous wave excitation. More generally, this work demonstrates the usefulness of resonance Raman as a characterization tool when characterizing adsorbed molecular species on semiconductor NC surfaces.