Charge transfer as a ubiquitous mechanism in determining the negative charge at hydrophobic interfaces

Abstract The origin of the apparent negative charge at hydrophobic–water interfaces has fueled debates in the physical chemistry community for decades. The most common interpretation given to explain this observation is that negatively charged hydroxide ions (OH – ) bind strongly to the interfaces. Using first principles calculations of extended air–water and oil–water interfaces, we unravel a mechanism that does not require the presence of OH – . Small amounts of charge transfer along hydrogen bonds and asymmetries in the hydrogen bond network due to topological defects can lead to the accumulation of negative surface charge at both interfaces. For water near oil, some spillage of electron density into the oil phase is also observed. The computed surface charge densities at both interfaces is approximately $$-0.015\ {\rm{e}}/{{\rm{nm}}}^{2}$$ − 0.015 e ∕ nm 2 in agreement with electrophoretic experiments. We also show, using an energy decomposition analysis, that the electronic origin of this phenomena is rooted in a collective polarization/charge transfer effect.