Predicting reaction barriers in solid-state systems under stress via second-order energy expansion

Abstract

Solid-state transformations are important in many areas of science and technology. Herein, a model for predicting the relative energies of stationary points along the reaction pathways for stress-induced solid-state transformations is assessed and applied. The model is based on a second-order expansion of the energy of the system with respect to changes in the unit cell, and requires a small number of parameters that can be obtained through quantum chemical calculations. Comparison of the model with the results of quantum chemical calculations indicates that the model accurately reproduces changes in energy occurring during stress-induced transformations over a reasonable range of stresses. A procedure for applying the model to identify stress tensors that are most likely to promote a desired reaction is illustrated. The results also indicate that this procedure provides insight into the connection between the form of a stress tensor and the changes in energy occurring during a stress-induced solid-state transformation.