Relativistic Jahn-Teller effect in tetrahedral systems

Journal Article · Thu Apr 15 04:00:00 EDT 2010 · Physical Review. A

DOI:https://doi.org/10.1103/PHYSREVA.81.042501· OSTI ID:21408591

Opalka, Daniel; Domcke, Wolfgang ^[1]; Segado, Mireia; Poluyanov, Leonid V ^[2]

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1. Department of Chemistry, Technische Universitaet Muenchen, D-85747 Garching (Germany)
2. 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, Journal Name: Physical Review. A Journal Issue: 4 Vol. 81; ISSN 1050-2947; ISSN PLRAAN
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
ANGULAR MOMENTUM
CATIONS
CHARGED PARTICLES
COUPLING
COUPLINGS
ELECTRONIC STRUCTURE
ENERGY RANGE
HAMILTONIANS
INTERMEDIATE COUPLING
IONS
JAHN-TELLER EFFECT
L-S COUPLING
MATHEMATICAL OPERATORS
ORIGIN
PARTICLE PROPERTIES
QUANTUM OPERATORS
RELATIVISTIC RANGE
SPIN
SYMMETRY