First principles study of a sodium borosilicate glass-former II: The glass state

TL;DR

This study uses ab initio simulations to analyze the structure, electronic, vibrational, and dielectric properties of a sodium borosilicate glass, revealing detailed atomic arrangements and spectral features linked to specific structural units.

Contribution

It provides a comprehensive first-principles analysis of the atomic structure and spectroscopic properties of sodium borosilicate glass, including the distribution of boron units and sodium atoms, and their influence on electronic and vibrational spectra.

Findings

Boron units involve non-bridging oxygens and have distinct spectral features.

Sodium atoms distribute differently around [3]B and [4]B units, affecting local structure.

Spectral features can identify boron structural units and their local environment.

Abstract

We use ab initio simulations to investigate the properties of a sodium borosilicate glass of composition 3Na_2O-B_2O_3-6SiO_2. We find that the broadening of the first peak in the radial distribution functions g_BO(r) and g_BNa(r) is due to the presence of trigonal and tetrahedral boron units as well as to non-bridging oxygen atoms connected to BO_3 units. In agreement with experimental results we find that the [3]B units involve a significant number of non-bridging oxygens whereas the vast majority of [4]B have only bridging oxygens. We determine the three dimensional distribution of the Na atoms around the [3]B and [4]B units and use this information to explain why the sodium atoms associated to the latter share more oxygen atoms with the central boron atoms than the former units. From the distribution of the electrons we calculate the total electronic density of states as well its decomposition into angular momentum contributions. The vibrational density of states shows at high frequencies a band that originates from the motion of the boron atoms. Furthermore we show that the [3]B and [4]B units give rise to well defined features in the spectrum which thus can be used to estimate the concentration of these structural entities. The contribution of [3]B can be decomposed further into symmetric and asymmetric parts that can also be easily identified in the spectrum. We show that certain features in the spectrum can be used to obtain information on the type of atom that is the second nearest neighbor of a boron in the [4]B unit. We calculate the average Born charges on the bridging and non-bridging oxygen atoms and show that these depend linearly on the angle between the two bonds and the distance from the connected cation, respectively. Finally we have calculated the frequency dependence of the dielectric function as well as the absorption spectra.