Direct measurement of resonance Raman spectra and cross sections by a polarization difference technique

Resonant Raman (RR) spectroscopy, despite its many promising applications in analytical chemistry and biology, remains an experimental challenge (compared to standard Raman) primarily because of the presence of large fluorescence backgrounds overwhelming the RR signals. The observation of RR spectra of fluorophores therefore requires the use of specialized, picosecond-time-resolved setups. Here, we present and demonstrate a method, based on polarization-difference, by which RR spectra and cross sections can be measured using the most standard Raman setup with continuous wave excitation and CCD-based detection. The method is applied to the dyes Nile Blue and rhodamine 6G under resonant excitation. This work should open a new era in RR spectroscopy, where RR spectra can be routinely measured and studied with conventional Raman systems.