Four modifications of the Jahn–Teller effects. The problem of observables: spin–orbit interaction, tunneling splitting, and orientational polarization of solids†
Abstract
In a semi-review paper, we first show that Landau's fundamental idea of the origin of spontaneous symmetry breaking (SSB) in atomic matter due to electronic degeneracy, termed the Jahn–Teller effect (JTE) and further developed into the pseudo-JTE (PJTE), was appended recently with two more modifications, the hidden JTE (h-JTE) and hidden PJTE (h-PJTE). All four versions of JTEs are defined in the adiabatic approximation by their adiabatic potential energy surfaces (APES), which possess a common feature – the lack of a minimum in the high-symmetry configuration, thus confirming (and extending) the Landau idea of SSB. However, although serving as a qualitative indication of the SSB and consequent possible (virtual) properties of the system, the APES by themselves are not experimentally observable directly, and this important feature of JTEs is often ignored. Taking spin–orbit interaction as an example, we show that just perturbation of the APES does not reveal its observable reduction by the JTE, which emerges only after solving the Schrödinger equation with this APES. Following the multi-minimum nature of the latter, this leads to tunneling splitting of the vibrational states in the minima wells or over-the-barrier (hindered) rotations, resulting in novel properties, one of them being the reduction of the spin–orbit coupling. We demonstrate the methodology of solving such problems by using the example of electric field polarization of the BaTiO3 crystal, which leads to a novel effect: orientational polarization of solids.
- This article is part of the themed collection: Festschrift Wolfgang E. Ernst: Electronic & Nuclear Dynamics in Molecules, Clusters, and on Surfaces