Gibbs free-energy differences between polymorphs via a diabat approach.

Polymorph free-energy differences are critical to several applications. A recently proposed diabat interpolation framework estimated free-energy differences between polymorphs by quadratic interpolation of diabats. This work extends the Zwanzig-Bennett relation to the NPT ensemble so that the diabats directly give Gibbs free-energy differences. We also demonstrate how the approach can be used in cases where the diabats are not parabolic. We illustrate the diabat method for Gibbs free-energy difference of zirconium (BCC and HCP phases) and compare it with the conventional lattice switch Monte Carlo approach.