Charge Transfer as a Ubiquitous Mechanism in Determining the Negative Charge at Hydrophobic Interfaces (1904.05766v2)

Abstract: The origin of the apparent negative charge at hydrophobic-water interfaces has fueled one of the biggest debates in physical chemistry for several decades. The most common interpretation given to explain this observation is that negatively charged hydroxide ions (OH-) bind strongly to the interfaces. Here, using first principles calculations of the air-water and oil-water interfaces consisting of thousands of atoms, we unravel a mechanism that does not require the presence of OH-. We show that small amounts of charge transfer along hydrogen bonds and asymmetries in the hydrogen bond network, associated with local topological defects can lead to the accumulation of negative surface charge at both interfaces. For water near oil, we show that there is also some spillage of electron density into the oil leaving it negatively charged. The surface charge densities at both interfaces is computed to be approximately $-0.015$ 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 and charge transfer effect.