Multi-phonon Raman scattering in semiconductor nanocrystals: importance of non-adiabatic transitions

Multi-phonon Raman scattering in semiconductor nanocrystals is treated taking into account both adiabatic and non-adiabatic phonon-assisted optical transitions. Because phonons of various symmetries are involved in scattering processes, there is a considerable enhancement of intensities of multi-phonon peaks in nanocrystal Raman spectra. Cases of strong and weak band mixing are considered in detail. In the first case, fundamental scattering takes place via internal electron-hole states and is participated by sand d-phonons, while in the second case, when the intensity of the one-phonon Raman peak is strongly influenced by the interaction of an electron and of a hole with interface imperfections (e. g., with trapped charge), p-phonons are most active. Calculations of Raman scattering spectra for CdSe and PbS nanocrystals give a good quantitative agreement with recent experimental results. 78.30.-j, 63.20.Kr, 61.46.+w, 71.35.+z, 71.38.+i, 85.42.+m Typeset using REVTEX