A theoretical interpretation of the chemical shift of ²⁹Si NMR peaks in alkali borosilicate glasses

In ²⁹Si-NMR, it has so far been accepted that the chemical shifts of Qⁿ species (SiO₄ units containing n bridging oxygens) were equivalent between alkali borosilicate and boron-free alkali silicate glasses. In the sodium borosilicate glasses with low sodium content, however, a contradiction was confirmed in the estimation of alkali distribution; ¹¹B NMR suggested that Na ions were entirely distributed to borate groups to form BO₄ units, whereas a -90 ppm component was also observed in ²⁹Si-NMR spectra, which has been attributed to Q³ species associated with a nonbridging oxygen (NBO). Then, cluster molecular orbital calculations were performed to interpret the -90 ppm component in the borosilicate glasses. It was found that a silicon atom which had two tetrahedral borons (B4) as its second nearest neighbors was similar in atomic charge and Si2p energy to the Q³ species in boron-free alkali silicates. Unequal distribution of electrons in Si-O-B4 bridging bonds was also found, where much electrons were localized on the Si-O bonds. It was finally concluded that the Si-O-B4 bridges with narrow bond angle were responsible for the -90 ppm ²⁹Si component in the borosilicate glasses. There still remained another interpretation; the Q³ species were actually present in the glasses, and NBOs in the Q³ species were derived from the tricluster groups, such as (O₃Si)O(BO₃)₂. In the glasses with low sodium content, however, it was concluded that the tricluster groups were not so abundant to contribute to the -90 ppm component.