Interfacial Effects on the Band Edges of Functionalized Si Surfaces in Liquid Water Tuan Anh Pham Donghwa Lee Eric Schwegler Giulia Galli 10.1021/ja5079865.s001 https://acs.figshare.com/articles/journal_contribution/Interfacial_Effects_on_the_Band_Edges_of_Functionalized_Si_Surfaces_in_Liquid_Water/2045247 By combining <i>ab initio</i> molecular dynamics simulations and many-body perturbation theory calculations of electronic energy levels, we determined the band edge positions of functionalized Si(111) surfaces in the presence of liquid water, with respect to vacuum and to water redox potentials. We considered surface terminations commonly used for Si photoelectrodes in water splitting experiments. We found that, when exposed to water, the semiconductor band edges were shifted by approximately 0.5 eV in the case of hydrophobic surfaces, irrespective of the termination. The effect of the liquid on band edge positions of hydrophilic surfaces was much more significant and determined by a complex combination of structural and electronic effects. These include structural rearrangements of the semiconductor surfaces in the presence of water, changes in the orientation of interfacial water molecules with respect to the bulk liquid, and charge transfer at the interfaces, between the solid and the liquid. Our results showed that the use of many-body perturbation theory is key to obtain results in agreement with experiments; they also showed that the use of simple computational schemes that neglect the detailed microscopic structure of the solid–liquid interface may lead to substantial errors in predicting the alignment between the solid band edges and water redox potentials. 2015-12-17 06:17:45 Interfacial Effects Si photoelectrodes 0.5 eV Functionalized Si Surfaces band edge positions semiconductor band edges water molecules semiconductor surfaces band edges Band Edges Liquid WaterBy charge transfer ab initio energy levels surface terminations dynamics simulations water redox potentials water splitting experiments