Investigation of lattice dynamics by means of vibronic spectra

Abstract

Electronic transitions at a foreign probe ion in a lattice exhibit vibrational sidebands. They may be used as a new tool to investigate lattice dynamics. To make this too effective the theory of vibronic spectra has been refined. The principal refinement is that of a partial Born-Oppenheimer approximation which establishes a rigid coupling of the electronic wavefunctions of the foreign ion to its own nucleus. The structural form of the one-phonon sideband is given as a projection of the classical Greens' function (imaginary part) onto single multipole-fields in lattice space. Employing a variety of electronic transitions and by careful group-theoretical analysis a complete irreducible sequence of projections can be extracted from the experiments. These functional forms depend sensibly on the eigenvectors of the lattice modes, whence they contain information, which cannot be received from neutron scattering. Moreover, the spectra related to the higher multipoles give insight into the disturbed (local) dynamics, whereas the lower type spectra concern the undisturbed (ideal) one. Systems, where the foreign probe ion has high symmetry, are most suitable for the new method. For systems of low local symmetry approximations are suggested by the low-frequency behaviour of the measured one-phonon band. Because of the high resolution of optical measurements, the information from vibronic spectra is comparable or even superior in detailed richness to neutron scattering data.