Multiphonon resonant Raman scattering predicted in (formula presented) from the Franck-Condon process via self-trapped excitons

Resonant behavior of the Raman process is predicted when the laser frequency is close to the orbital excitation energy of (formula presented) at 2 eV. The incident photon creates a vibrationally excited self-trapped “orbiton” state from the orbitally ordered Jahn-Teller (JT) ground state. Trapping occurs by local oxygen rearrangement. Then the Franck-Condon mechanism activates multiphonon Raman scattering. The amplitude of the n-phonon process is first order in the electron-phonon coupling g. The resonance occurs via a dipole forbidden d to d transition. We previously suggested that this transition (also seen in optical reflectivity) becomes allowed because of asymmetric oxygen fluctuations. Here we calculate the magnitude of the corresponding matrix element using local spin-density functional theory. This calculation agrees to better than a factor of two with our previous value extracted from experiment. This allows us to calculate the absolute value of the Raman tensor for multiphonon scattering. Observation of this effect would be a direct confirmation of the importance of the JT electron-phonon term and the presence of self-trapped orbital excitons, or “orbitons.”