Generation of Amorphous Silica Surfaces with Controlled Roughness

NP Nguyen and BB Laird, JOURNAL OF PHYSICAL CHEMISTRY A, 127, 9831-9841 (2023).

DOI: 10.1021/acs.jpca.3c04955

Amorphous silica (a-SiO2) surfaces, when grafted with select metals on the active sites of the functionalized surfaces, can act as useful heterogeneous catalysts. From a molecular modeling perspective, one challenge has been generating a-SiO2 slab models with controllable surface roughness to facilitate the study of the effect of surface morphology on the material properties. Previous computational methods either generate relatively flat surfaces or periodically corrugated surfaces that do not mimic the full range of potential surface roughness of the amorphous silica material. In this work, we present a new method, inspired by the capillary fluctuation theory of interfaces, in which rough silica slabs are generated by cleaving a bulk amorphous sample using a cleaving plane with Fourier components randomly generated from a Gaussian distribution. The width of this Gaussian distribution (and thus the degree of surface roughness) can be tuned by varying the surface roughness parameter alpha. Using the van Beest, Kramer, and van Santen (BKS) force field, we create a large number of silica slabs using cleaving surfaces of varying roughness (alpha) and using two different system sizes. These surfaces are then characterized to determine their roughness (mean-squared displacement), density profile, and ring size distribution. This analysis shows a higher concentration of surface defects (under-/overcoordinated atoms and strained rings) as the surface roughness increases. To examine the effect of the roughness on surface reactivity, we re-equilibriate a subset of these slabs using the reactive force field ReaxFF and then expose the slabs to water and observe the formation of surface silanols. We observe that the rougher surfaces exhibit higher silanol concentrations as well as bimodal acidity.

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