pH dependent reactivity of boehmite surfaces from first principles molecular dynamics.

pH dependent interfacial chemistry depends upon the distribution and respective pKa values of different surface active sites. This is highly relevant to the chemistry of nanoparticle morphologies that expose faces with varying surface termination. Recent synthetic advances for nanoparticles of various minerals, including AlO(OH) (boehmite), present an excellent opportunity to compare and contrast predicted surface pKa on low Miller index planes so as to reinterpret reported interfacial properties (i.e., point of zero charge - PZC) and reactivity. This work employs ab initio molecular dynamics and empirical models to predict site-specific pKa values of accurate (benchmarked) surface models of boehmite. Using the different surface site populations, the PZC is determined and the influence this has upon reported interfacial chemistry is described.