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Resonance Raman spectra have been obtained from dilute solutions of ferri-hemoglobin fluoride, using several Ar+ laser lines, as well as the 6328 8, He-Ne line, for excitation. Several modes (including some with inverse polarization) correspond to vibrations which mix the first two n -z * porphyrin transitions, and their excitation profiles confirm the assignment of the lower of these transitions to a band, at 5280 A, which is unresolved in the room-temperature absorption spectrum.Resonance enhancement of porphyrin modes with 6328 8, excitation suggests substantial mixing of the lower n-n* transition with porphyrin-metal charge transfer transitions, which presumably account for the low energy visible bands. Totally symmetric modes are observed which come into resonance with the intense near-ultraviolet (Soret) transition. The most intense of these, at 1373 cm-1 accurately obeys the frequency dependence expected for a mode which couples to a single electronic transition.

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