The (E + A) (e + a) Jahn-Teller and pseudo-Jahn-Teller Hamiltonian including spin-orbit coupling for trigonal systems. Academic Article uri icon


  • The Hamiltonian describing E e Jahn-Teller (JT) coupling and (E + A) (e + a) pseudo-JT (PJT) coupling is developed beyond the standard JT theory for the example of XY3 systems, taking the bending modes of a and e symmetry into account. For the electrostatic (spin-free) Hamiltonian, the conventional Taylor expansion up to second order in symmetry-adapted displacements is replaced by an expansion in invariant polynomials up to arbitrarily high orders. The relevance of a systematic high-order expansion in the three large-amplitude bending modes is illustrated by the construction of an eighth-order three-sheeted three-dimensional ab initio potential-energy surface for PH3+. The theory of spin-orbit coupling in trigonal JT/PJT systems is extended beyond the standard model of JT theory by an expansion of the microscopic Breit-Pauli operator up to second order in symmetry-adapted vibrational coordinates. It is shown that a linear E e JT effect of relativistic origin exists in C(3v) systems which vanishes at the planar (D(3h)) geometry. The linear relativistic 2E 2A PJT coupling, on the other hand, persists at the planar geometry

published proceedings

  • J Phys Chem A

author list (cited authors)

  • Bhattacharyya, S., Opalka, D., Poluyanov, L. V., & Domcke, W.

publication date

  • January 1, 2014 11:11 AM