4.7 Article

Relativistic ExT Jahn-Teller effect in tetrahedral systems

Journal

JOURNAL OF CHEMICAL PHYSICS
Volume 129, Issue 22, Pages -

Publisher

AMER INST PHYSICS
DOI: 10.1063/1.3035189

Keywords

Jahn-Teller effect; potential energy functions; potential energy surfaces; relativistic corrections; spin-orbit interactions; wave functions

Funding

  1. Deutsche Forschungsgemeinschaft

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It is shown that (2)E states in tetrahedral systems exhibit a linear ExT Jahn-Teller effect which is of purely relativistic origin (that is, it arises from the spin-orbit-coupling operator). The electrostatic interactions give rise to a Jahn-Teller effect which is quadratic in the T displacements. The 4x4 Hamiltonian matrix in a diabatic spin-electron basis is derived by an expansion of the electrostatic electronic Hamiltonian and the Breit-Pauli spin-orbit operator in powers of the Jahn-Teller active normal mode and taking account of symmetry selection rules for the matrix elements. The adiabatic potential-energy functions of the (2)ExT system are doubly degenerate (Kramers degeneracy). For small displacements from the tetrahedral reference geometry, the adiabatic potential-energy surfaces represent a double cone in four-dimensional space, which is a novel topography of Jahn-Teller potential-energy surfaces. The topological phases of the adiabatic electronic wave functions are discussed.

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