THEORY OF RESONANCE RAMAN OPTICAL-ACTIVITY - THE SINGLE ELECTRONIC-STATE LIMIT

The theory of natural Raman optical activity (ROA) is extended to the limit of strong resonance with a single electronic state (SES). It is shown that in the SES limit, the resonance ROA (RROA) bands all have t he same sign, and their relative intensities are identical to the corr esponding resonance Raman (RR) parent bands. The sign of the RROA band s are predicted to be opposite that of the pure electronic circular di chroism (CD) of the single, resonant electronic transition, The ratio of the RROA to the RR spectrum is the same or one-half the magnitude o f the electronic CD anisotropy ratio of the resonant electronic state. Deviation from this simple pattern is indicative of contributions fro m more than one excited electronic state to the RR and RROA spectra, a nd hence is a sensitive probe of the electronic origin of ordinary RR spectra.