Theoretical exploration of the relativistic Jahn-Teller effect

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This project is part of a long-term effort to explore the Jahn-Teller forces in molecules, clusters and coordination complexes which arise from the spin-orbit operator and are, therefore, of relativistic origin. Jahn-Teller Hamiltonians including novel relativistic coupling terms will be derived for trigonal, tetragonal, cubic and octahedral systems using group-theoretical methods. In addition to the perturbative description of spin-orbit coupling via the Breit-Pauli operator, which is appropriate for systems containing light and moderately heavy elements, a systematic theory of the Jahn-Teller effect is developed which is based on a variational treatment of relativistic effects in electronic-structure theory and is appropriate for systems containing very heavy elements. Electrostatic and relativistic Jahn-Teller coupling parameters will be determined with ab initio electronic-structure calculations for selected groups of molecules and clusters, e.g. transition-metal trifluorides and hexafluorides as well as cluster cations of the fourth and fifth main group. Vibrational and electronic Jahn-Teller spectra will be computed for these systems with ab initio based Jahn-Teller Hamiltonians.