Charge Transfer into Organic Thin Films: A Deeper Insight through Machine‐Learning‐Assisted Structure Search

Density functional theory calculations are combined with machine learning to investigate the coverage-dependent charge transfer at the tetracyanoethylene/Cu(111) hybrid organic/inorganic interface. The study finds two different monolayer phases, which exhibit a qualitatively different charge-transfer behavior. Our results refute previous theories of long-range charge transfer to molecules not in direct contact with the surface. Instead, they demonstrate that experimental evidence supports our hypothesis of a coverage-dependent structural reorientation of the first monolayer. Such phase transitions at interfaces may be more common than currently envisioned, beckoning a thorough reevaluation of organic/inorganic interfaces.