Size-Dependent Ab Initio Atomistic Thermodynamics from Cluster to Bulk: Application to Hydration of Titania Nanoparticles

Abstract

Ab initio atomistic thermodynamics (AIAT) has become an indispensable tool to estimate Gibbs free energy changes for solid surfaces interacting with gaseous species relative to pressure ( p ) and temperature ( T ). For such systems, AIAT assumes that solid vibrational contributions to Gibbs free energy differences cancel out. However, the validity of this assumption is unclear for nanoscale systems. Using hydrated titania nanoparticles (NPs) as an example, we estimate the vibrational contributions to the Gibbs free energy of hydration (Δ G hyd ( T , p )) for arbitrary NP size and degree of hydration. Comparing Δ G hyd ( T , p ) phase diagrams for NPs when considering these contributions (AIAT nano ) relative to a standard AIAT approach reveals significant qualitative and quantitative differences, which only become negligible for large systems. By constructing a size-dependent Δ G hyd ( T , p ) phase diagram, we illustrate how our approach can provide deeper insights into how nanosytems interact with their environments, with many potential applications (e.g., catalytic nanoparticles, biological colloids, nanoparticulate pollutants).