Relativistic theory of the Jahn-Teller effect: p-orbitals in tetrahedral and trigonal systems
- Department of Chemistry, Technische Universität München, D-85747 Garching (Germany)
- Max-Planck-Institut für Festkörperforschung, Stuttgart (Germany)
- Institute of Chemical Physics, Academy of Sciences, Chernogolovka, Moscow 142432 (Russian Federation)
A relativistic generalization of Jahn-Teller theory is presented which includes spin-orbit coupling effects beyond low-order Taylor expansions in vibrational coordinates. For the example of a p-electron in tetrahedral and trigonal environments, the matrix elements of the Breit-Pauli spin-orbit-coupling operator are expressed in terms of the matrix elements of the electrostatic electronic potential. Employing expansions of the latter in invariant polynomials in symmetry-adapted nuclear coordinates, the spin-orbit induced Jahn-Teller coupling terms are derived for the T{sub 2} × (t{sub 2} + e) and (E + A) × (e + a) Jahn-Teller problems up to arbitrarily high orders. The linear G{sub 3/2} × (t{sub 2} + e) Jahn-Teller Hamiltonian of Moffitt and Thorson [Phys. Rev. 108, 1251 (1957)] for tetrahedral systems is generalized to higher orders in vibrational displacements. The Jahn-Teller Hamiltonians derived in the present work are useful for the interpolation and extrapolation of Jahn-Teller distorted potential-energy surfaces of molecules and complexes with heavy elements as well as for the calculation of vibronic spectra of such systems.
- OSTI ID:
- 22657839
- Journal Information:
- Journal of Chemical Physics, Vol. 144, Issue 12; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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