Van Vleck Analysis of Angularly Distorted Octahedra using VanVleckCalculator

TL;DR

This paper introduces a new method and Python tool for accurately calculating Van Vleck modes in angularly distorted octahedra, improving analysis of Jahn-Teller distortions by including shear and angular effects.

Contribution

A novel approach and software implementation for calculating Van Vleck modes without ignoring angular distortions in octahedra.

Findings

Van Vleck modes can be calculated considering angular distortion.

Octahedral shear and angular distortion are often correlated.

The shear fraction parameter $ta$ predicts correlation under varying conditions.

Abstract

Van Vleck modes describe all possible displacements of octahedrally-coordinated ligands about a core atom. They are a useful analytical tool for analysing the distortion of octahedra, particularly for the first-order Jahn-Teller distortion. Determination of Van Vleck modes of an octahedron is complicated by the presence of angular distortion of octahedra however. This problem is most commonly resolved by calculating the bond distortion modes ($Q_2$, $Q_3$) along the bond axes of the octahedron, disregarding the angular distortion and losing information on the octahedral shear modes ($Q_4$, $Q_5$, and $Q_6$) in the process. In this paper, the validity of assuming bond lengths to be orthogonal in order to calculate the van Vleck modes is discussed, and a method is described for calculating Van Vleck modes without disregarding the angular distortion. A Python code for doing this, VanVleckCalculator, is introduced, and some examples of its use are given. Finally, we show that octahedral shear and angular distortion are often, but not always, correlated, and propose a parameter as the shear fraction, $\eta$. We demonstrate that $\eta$ can be used to predict whether the values will be correlated when varying a tuning parameter such as temperature or pressure.