Iron and oxygen vacancies at the hematite surface: pristine case and with a chlorine adatom

Defect complexes play critical roles in the dynamics of water molecules in photoelectrochemical cell devices. For the specific case of hematite (α-Fe₂O₃), iron and oxygen vacancies are said to mediate the water splitting process through the localization of optically-derived charges. Using first-principles methods based on density-functional theory we show that both iron and oxygen vacancies can be observed at the surface. For an oxygen-rich environment, usually under wet conditions, the charged iron vacancies should be more frequent. As sea water would be an ideal electrolyte for this kind of device, we have also analyzed the effect of additional chlorine adsorption on this surface. While the chlorine adatom kills the charged oxygen vacancies, entering the void sites, it will not react with the iron vacancies, keeping them active during water splitting processes.