Predicting large-supercell defect formation energies from machine-learning charge density models trained on small supercells

Abstract

First-principles defect calculations are often limited by the cost of the large supercells required to suppress image interactions. Machine-learning interatomic potentials (MLIPs) provide another alternative, but training defect MLIPs typically requires thousands of structures and weeks of data generation. Since charge density is the key to density-functional-theory (DFT), we propose a machine-learning charge density (MLCD) route for predicting defect formation energies with higher data efficiency. We optimize the training set by integrating small supercells of varying sizes for better extrapolation, allocating their proportions based on spatial charge-density analysis. With only 96 supercells containing 16--96 atoms as the dataset, MLCD accurately predicts the formation energies of four intrinsic defects in 360-atom supercells, with defect-wise mean absolute error below 0.05 eV. In contrast, MLIPs trained on the same dataset can err by more than 1 eV. These results show that charge-density learning enables more robust cross-size transfer than direct energy-force fitting and that mixed-size data design can substantially reduce the cost of defect prediction.