The electrostatic potential derived from the quantum mechanical charge density plays an important role in several fields including materials science and can be accessed by means of ab-initio calculations. Averages of of this electrostatic potential can be measured with electron diffraction/holography and the bulk average is called the mean inner potential (MIP). These experimental techniques have also proven very useful to study the impact of bonding in chemical systems. A better understanding of concentrated NaCl electrolytes and the distribution of voltages inside them is highly desirable given the availability of experimental techniques such as cryoholography and the relevance of ionic solutions for biological systems. We find excellent agreement with experimental data on the MIP of vitrified water and NaCl crystals and demonstrate the impact of covalent bonding in water and intermolecular interactions between them as well as ionic bonding in NaCl crystals on it. The remarkable connection between the MIP and the diamagnetic susceptibility is used for an additional comparison with experiment and has the potential for deepening the understanding of proton NMR chemical shifts. Furthermore the distributions and fluctuations of the potentials inside aqueous NaCl electrolytes are characterized predicting a qualitative jump in the distributions of measured potentials once the resolution limits in electron holography tomography are pushed beneath molecular resolution.

Ab-initio electrostatic potentials and mean inner potentials of concentrated NaCl<sub>aq</sub>

248th National Meeting (2014)

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Ab-initio electrostatic potentials and mean inner potentials of concentrated NaClaq

Ab-initio electrostatic potentials and mean inner potentials of concentrated NaCl_aq