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

Authors
Type
Published Article
Journal
The Journal of Physical Chemistry A
1520-5215
Publisher
American Chemical Society
Publication Date
Volume
118
Issue
51
Pages
11962–11970
Identifiers
DOI: 10.1021/jp506793z
PMID: 25207676
Source
Medline

Abstract

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

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