Multi-scale dynamics at the glassy silica surface.

Silica-based glass is a household name, providing insulation for windows to microelectronics. The debate over the types of motions thought to occur in or on SiO2 glass well below the glass transition temperature continues. Here, we form glassy silica films by oxidizing the Si(100) surface (from 0.5 to 1.5 nm thick, to allow tunneling). We then employ scanning tunneling microscopy in situ to image and classify these motions at room temperature on a millisecond to hour time scale and 50-pm to 5-nm length scale. We observe two phenomena on different time scales. Within minutes, compact clusters with an average diameter of several SiO2 glass-forming units (GFUs) hop between a few (mostly two) configurations, hop cooperatively (facilitation), and merge into larger clusters (aging) or split into smaller clusters (rejuvenation). Within seconds, Si-O-Si bridges connect two GFUs within a single cluster flip, providing a vibrational fine structure to the energy landscape. We assign the vibrational fine structure using electronic structure calculations. Calculations also show that our measured barrier height for whole cluster hopping at the glass surface (configurational dynamics) is consistent with the configurational entropy predicted by thermodynamic models of the glass transition and that the vibrational entropy for GFU flipping and configurational entropy for cluster hopping are comparable (on a per GFU basis).