Mean Inner Potential of Liquid Water

Water Breakup at Fe2O3–Hematite/Water Interfaces: Influence of External Electric Fields from Nonequilibrium Ab Initio Molecular Dynamics

“…The profile of the Hartree potential across the whole supercell can be seen in Figure S5 of the Supporting Information , where the large interfacial potential drop is noticeable. The potential difference between the bulk hematite and bulk water was found to be 10.5 V, which is consistent with mean-inner-potential (MIP) values previously published in the literature: the experimental MIP of liquid water is 4.5 V, 70 while the values for hematite are estimated to be in a range between 16.2 and 19.5 V. 71 Althought the potential values are very large, the external fields induce dramatic changes, in particular at the antiparallel interface, representing the positively charged anode. This is connected with proton adsorption and corresponding charge redistribution on these interfaces, in accordance with the previous discussion.…”

Deciphering second harmonic generation signals

“…[39][40][41][42][43][44][45][46] Moreover, when the bulk quadrupole contribution is included, the permanent polarisation term along the z-axis, P (0) s,z , represents an inner potential of -4.0991 V (see Table S3), which is in very good agreement with the value of 3.87 V calculated by Remsing and coworkers 47 using DFT and with the value of 4.48 V determined experimentally by Yesibolati and co-workers. 48 P (0) s,z is already nonzero when the dipole contribution only is considered but leads to a correct inner electric potential of water at the air/water interface only when the bulk quadrupole contribution is included.…”

The Born model can accurately describe electrostatic ion solvation

“…This corresponds to setting the zero of the electrostatic potential to be the average value in bulk water. The average potential inside pure water is determined by the internal structure of the water molecules and its true value is a very large positive value (3-5 V) [26][27][28] this leads to very unusual solvation free energies when the correct quantum mechanical value is used for this reference. It results in cations being massively favoured as the potential inside the cavity the ion occupies is very negative relative to this large positive reference.…”