Structure and sum-frequency generation spectra of water on uncharged Q4 silica surfaces: a molecular dynamics study

Abstract

The structural characteristics and sum-frequency generation (SFG) spectra of water near neutral Q₄ silica surfaces were investigated by molecular dynamics simulations. The interactions of water molecules with atoms of the solid were described by different potential models, in particular by the CLAYFF [Cygan et al., J. Phys. Chem. B, 2004, 108, 1255] and INTERFACE [Heinz et al. Langmuir, 2013, 29, 1754] force fields. The calculations of the contact angle of water have shown that the silica surface modeled with CLAYFF behaves as macroscopically hydrophilic, in contrast to the surface described with the INTERFACE model. The hydrophilicity of CLAYFF stems from too attractive electrostatic surface–water interactions. Regardless of the surface's affinity for water, the aqueous phase has a layered structure in the direction perpendicular to the surface with density fluctuations decaying within a distance of 10 Å from the surface. The orientational ordering of H₂O molecules was found to be more short-range than the density fluctuations, especially for the hydrophobic surfaces. Modeling the SFG spectra has shown that the spectra of all studied hydrophobic silica–water interfaces are similar and have features in common with the spectrum of the water–vapor interface. The spectra fairly agree with experimental results obtained for the silica–water interface at low pH conditions [Myalitsin et al., J. Phys. Chem. C, 2016, 120, 9357]. The spectral response for the hydrophobic interface was computed to primarily arise from the topmost molecules of the first layer of interfacial water. In contrast, the SFG signal from the hydrophilic silica–water interface is accumulated over a greater distance extending for several water layers due to more long-range perturbation of the structure by the surface.