Numerical adiabatic potentials of orthorhombic Jahn-Teller effects retrieved from ultrasound attenuation experiments. Application to the SrF2:Cr crystal

TL;DR

This paper develops a method to extract detailed parameters of a six-dimensional adiabatic potential energy surface for Jahn-Teller systems from ultrasound attenuation experiments, demonstrated on SrF2:Cr crystals.

Contribution

It introduces a novel approach combining ultrasound data with theoretical analysis to determine all key parameters of the APES in Jahn-Teller systems.

Findings

Identified orthorhombic minima as global minima on the APES.

Estimated all vibronic coupling constants and force constants.

Determined energy barriers and tunneling splittings for the system.

Abstract

A methodology is worked out to retrieve the numerical values of all the main parameters of the six-dimensional adiabatic potential energy surface (APES) of a polyatomic system with a quadratic T-term Jahn-Teller effect (JTE) from ultrasound experiments. The method is based on a verified assumption that ultrasound attenuation and speed encounter anomalies when the direction of propa- gation and polarization of its wave of strain coincides with the characteristic directions of symmetry breaking in the JTE. For the SrF2:Cr crystal, employed as a basic example, we observed anomaly peaks in the temperature dependence of attenuation of ultrasound at frequencies of 50-160 MHz in the temperature interval of 40-60 K for the wave propagating along the [110] direction, for both the longitudinal and shear modes, the latter with two polarizations along the [001] and [110] axes, respectively. We show that these anomalies are due to the ultrasound relaxation by the system of non-interacting Cr2+ JT centers with orthorhombic local distortions. The interpretation of the ex- perimental findings is based on the T2g (eg +t2g) JTE problem including the linear and quadratic terms of vibronic interactions in the Hamiltonian and the same-symmetry modes reduced to one interaction mode. Combining the experimental results with a theoretical analysis we show that on the complicated six-dimensional APES of this system with three tetragonal, four trigonal, and six orthorhombic extrema points, the latter are global minima, while the former are saddle points, and we estimate numerically all the main parameters of this surface, including the linear and quadratic vibronic coupling constants, the primary force constants, the coordinates of all the extrema points and their energies, the energy barrier between the orthorhombic minima, and the tunneling splitting of the ground vibrational states.