Structure and vibrational properties of sodium silicate glass surfaces

Abstract

Using molecular dynamics simulations, we investigate how the structural and vibrational properties of the surfaces of sodo-silicate glasses depend on the sodium content as well as the nature of the surface. Two types of glass surfaces are considered: A melt-formed surface (MS) in which a liquid with a free surface has been cooled down into the glass phase and a fracture surface (FS) obtained by tensile loading of a glass sample. We find that the MS is more abundant in Na and non-bridging oxygen atoms than the FS and the bulk glass, whereas the FS has higher concentration of structural defects such as two-membered rings and under-coordinated Si than the MS. We associate these structural differences to the production histories of the glasses and the mobility of the Na ions. It is also found that for Na-poor systems, the fluctuations in composition and local atomic charge density decay with a power-law as a function of distance from the surface, while Na-rich systems show an exponential decay with a typical decay length of ≈2.3 Å. The vibrational density of states shows that the presence of the surfaces leads to a decrease in the characteristic frequencies in the system. The two-membered rings give rise to a pronounce band at ≈880 cm−1, which is in good agreement with experimental observations.