Experiment-Driven Atomistic Materials Modeling: A Case Study Combining X-Ray Photoelectron Spectroscopy and Machine...

An important yet challenging aspect of atomistic materials modeling is reconciling experimental and computational results. Conventional approaches involve generating numerous configurations through molecular dynamics or Monte Carlo structure optimization and selecting the one with the closest match to experiment. However, this inefficient process is not guaranteed to succeed. We introduce a general method to combine atomistic machine learning (ML) with experimental observables that produces atomistic structures compatible with experiment by design. We use this approach in combination with grand-canonical Monte Carlo within a modified Hamiltonian formalism, to generate configurations that agree with experimental data and are chemically sound (low in energy). We apply our approach to understand the atomistic structure of oxygenated amorphous carbon (a-CO), an intriguing carbon-based material, to answer the question of how much oxygen can be added to carbon before it fully decomposes into CO and CO₂. Utilizing an ML-based X-ray photoelectron spectroscopy (XPS) model trained from GW and density functional theory (DFT) data, in conjunction with an ML interatomic potential, we identify a-CO structures compliant with experimental XPS predictions that are also energetically favorable with respect to DFT. Employing a network analysis, we accurately deconvolve the XPS spectrum into motif contributions, both revealing the inaccuracies inherent to experimental XPS interpretation and granting us atomistic insight into the structure of a-CO. This method generalizes to multiple experimental observables and allows for the elucidation of the atomistic structure of materials directly from experimental data, thereby enabling experiment-driven materials modeling with a degree of realism previously out of reach.