Observation of resonance electronic and non-resonance-enhanced vibrational natural Raman optical activity

Natural resonance electronic Raman optical activity (ROA) is observed for the first time. Coincidently, the first example of vibrational ROA enhanced by low‐lying electronic transition is reported. These new phenomena were measured using the rare‐earth complex Eu(tfc)3 (+)‐tris[3‐trifluoroacetyl‐D‐camphorato]europium(III), where electronic resonance occurs between the 532‐nm laser excitation and the 7F1 → 5D1 transition of the Eu3+ metal center. Electronic Raman spectra involve the Raman transitions terminating on the low‐lying electronic states of Eu(tfc)3. The observed vibrational ROA spectra are enhanced relative to typical ROA spectra by the proximity of vibrational states of Eu(tfc)3 to its low‐lying electronic states with significant magnetic‐dipole character, whereas the parent vibrational Raman spectra do not appear to be resonance‐enhanced since the 532‐nm vibrational Raman spectrum has similar relative intensities to the corresponding Raman spectrum measured with 1064‐nm laser excitation. Copyright © 2010 John Wiley & Sons, Ltd. Both the natural resonance electronic Raman optical activity (ROA), observed for the first time, and also the first example of vibrational ROA enhanced by low‐lying electronic transition are reported for the complex (+)‐Eu(tfc)3.