Relativistic Jahn-Teller effect in tetrahedral systems
- Department of Chemistry, Technische Universitaet Muenchen, D-85747 Garching (Germany)
- Institute of Chemical Physics, Academy of Sciences, Chernogolovka, Moscow RU-142432 (Russian Federation)
It is shown that orbitally degenerate states in highly symmetric systems are split by Jahn-Teller forces which are of relativistic origin (that is, they arise from the spin-orbit coupling operator). For the example of tetrahedral systems, the relativistic Jahn-Teller Hamiltonians of orbitally degenerate electronic states with spin 1/2 are derived. While both electrostatic and relativistic forces contribute to the Jahn-Teller activity of vibrational modes of E and T{sub 2} symmetry in {sup 2}T{sub 2} states of tetrahedral systems, the electrostatic and relativistic Jahn-Teller couplings are complementary for {sup 2}E states: The E mode is Jahn-Teller active through electrostatic forces, while the T{sub 2} mode is Jahn-Teller active through the relativistic forces. The relativistic Jahn-Teller parameters have been computed with ab initio relativistic electronic-structure methods. It is shown for the example of the tetrahedral cluster cations of the group V elements that the relativistic Jahn-Teller couplings can be of the same order of magnitude as the familiar electrostatic Jahn-Teller couplings for the heavier elements.
- OSTI ID:
- 21408591
- Journal Information:
- Physical Review. A, Vol. 81, Issue 4; Other Information: DOI: 10.1103/PhysRevA.81.042501; (c) 2010 The American Physical Society; ISSN 1050-2947
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
CATIONS
COUPLINGS
ELECTRONIC STRUCTURE
HAMILTONIANS
JAHN-TELLER EFFECT
L-S COUPLING
ORIGIN
RELATIVISTIC RANGE
SPIN
SYMMETRY
ANGULAR MOMENTUM
CHARGED PARTICLES
COUPLING
ENERGY RANGE
INTERMEDIATE COUPLING
IONS
MATHEMATICAL OPERATORS
PARTICLE PROPERTIES
QUANTUM OPERATORS