Systematic and accurate anharmonic formation free energies of metastable defects via a constrained Bayesian Adaptive Biasing Force framework

Abstract

Computing the formation free energies of metastable defects at finite temperature remains challenging due to anharmonicity, the multiplicity of basins and the frequent occurrence of migration events. Using the previously introduced constrained Bayesian Adaptive Biasing Force method (BABFc), we establish a practical thermodynamic integration framework for computing restricted anharmonic formation free energies associated with individual metastable defect basins. We demonstrate that BABFc can be exploited as a robust, systematic and numerically efficient tool for addressing a long standing bottleneck in atomistic materials science: the finite temperature thermodynamic characterization of metastable defects in complex, highly anharmonic energy landscapes. The proposed workflow requires only a reference local minimum and a confinement strategy and does not rely on defect specific collective variables. It therefore provides a general route to assign well-defined free energies to individual metastable basins, even when these basins are separated by low barriers and embedded in a dense landscape of competing configurations. In this setting, BABFc enables stable, bias corrected free energy estimates with statistical accuracies at the meV/atom level and a very low failure rate, including for systems containing approximately one thousand atoms. We demonstrate this capability through thousands of independent free energy calculations covering hundreds of four-interstitial and four-vacancy configurations in bcc $\alpha$-Fe over a broad temperature range, using both a traditional empirical potential and a data driven force field.