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Author Domcke, Wolfgang ♦ Opalka, Daniel ♦ Poluyanov, Leonid V.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword ATOMIC AND MOLECULAR PHYSICS ♦ JAHN-TELLER EFFECT ♦ L-S COUPLING ♦ MATRIX ELEMENTS ♦ POTENTIAL ENERGY ♦ RELATIVISTIC RANGE
Abstract 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.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2016-03-28
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 144
Issue Number 12


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