Nuclear Quantum Effects in Sodium Hydroxide Solutions from Neural Network Molecular Dynamics Simulations.

Abstract

Nuclear quantum effects (NQEs) cause the nuclei of light elements like hydrogen to delocalize, affecting numerous properties of water and aqueous solutions, such as hydrogen-bonding and proton transfer barriers. Here, we address the prototypical case of aqueous NaOH solutions by investigating the effects of quantum nuclear fluctuations on radial distribution functions, hydrogen-bonding geometries, power spectra, proton transfer barriers, proton transfer rates, water self-exchange rates around the Na+ cations, and diffusion coefficients, for the full room-temperature solubility range. These properties were calculated from classical and ring-polymer molecular dynamics simulations employing a reactive high-dimensional neural network potential based on dispersion-corrected density functional theory reference calculations. We find that NQEs have a very small impact on the solvation structure around Na+, slightly strengthen the water-water and water-hydroxide hydrogen bonds, and lower the peak positions in the power spectra for the HOH bending and OH stretching modes by about 50 and 100 cm-1, respectively. Moreover, NQEs significantly lower the proton transfer barriers, thus increasing the proton transfer rates, resulting in an increase of the diffusion coefficient in particular of OH-, as well as a decrease of the mean residence time of molecules in the first hydration shell around Na+ at high NaOH concentrations.