# Phase behaviour of empirical potentials of titanium dioxide

## TL;DR

This study compares the phase diagrams of original and reparameterised empirical potentials of titanium dioxide, revealing differences in stability regions and inconsistencies with experimental data.

## Contribution

It provides the first detailed phase diagram analysis of Lennard-Jones reparameterisations of the Matsui-Akaogi potential for TiO2.

## Key findings

- Both potentials support multiple crystalline polymorphs.
- The stability regions differ significantly between potentials.
- Neither potential fully matches experimental phase behaviour.

## Abstract

In recent years, several relatively similar empirical models of titanium dioxide have been proposed as reparameterisations of the potential of Matsui and Akaogi, with the Buckingham interaction replaced by a Lennard-Jones interaction. However, because of the steepness of the repulsive region of the Lennard-Jones potential, such reparameterised models result in rather different mechanical and thermodynamic properties compared to the original potential. Here, we use free-energy calculations based on the Einstein crystal method to compute the phase diagram of both the Matsui-Akaogi potential and one of its Lennard-Jones-based reparameterisations. Both potentials are able to support a large number of distinct crystalline polymorphs of titanium dioxide that have been observed in experiment, but the regions of thermodynamic stability of the individual phases are significantly different from one another. Moreover, neither potential results in phase behaviour that is fully consistent with the available experimental evidence.