Magnetic resonance‐Raman optical activity of ferrocytochrome c theory and experiment

The theory of magnetic resonance Raman optical activity in metal porphyrins is developed. Irreducible tensor methods are used to calculate the transition polarizabilities (involving both symmetric and antisymmetric contributions) which are formulated in terms of a vibronic development of the Raman transition tensors. The circular intensity difference for the vibrations of symmetry species A1, A2, B1 and B2 is explicitly evaluated for excitation within the 0–0 and 0–1 visible absorption bands. Polarized, depolarized and unpolarized magnetic resonance Raman optical activity spectra of ferrocytochrome c within the 0–0 and 0–1 bands are presented. Good qualitative agreement is found between theory and experiment.