Off-center impurity in alkali halides: reorientation, electric polarization and pairing to F center. I. Basic equations

TL;DR

This paper develops a vibronic theory for off-center Li+ impurities in alkali halides, analyzing their reorientation, polarization, and pairing with F centers, including potential energy barriers and vibrational effects.

Contribution

It derives analytical expressions for reorientation barriers and calculates higher-order electron-vibrational coupling constants for off-center impurities.

Findings

Derived periodic potential energy barriers for impurity reorientation.

Calculated third-order electron-vibrational coupling constants.

Identified vibrational frequency renormalization effects.

Abstract

Extending earlier work on a vibronic theory of the FA centers in alkali halides, the reorientation is now considered of an off-center Li+ impurity, either isolated or near an F center. We derive analytically periodic potential energy barriers between metastable reorientational off-center sites, the barriers hindering the impurity rotation around the normal lattice site. Applying to a specific model, electron-vibrational mode coupling constants are calculated up to 3rd order of the expansion of the coupling energy in the T1u mode coordinates. The 3rd order coupling brings about additional renormalization of the reorientation controlling vibrational frequency.