Size-Dependent Ab Initio Atomistic Thermodynamics from Cluster to Bulk: Application to Hydration of Titania Nanoparticles.
J Phys Chem Lett
; 15(32): 8240-8247, 2024 Aug 15.
Article
en En
| MEDLINE
| ID: mdl-39105711
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 (ΔGhyd(T,p)) for arbitrary NP size and degree of hydration. Comparing ΔGhyd(T,p) phase diagrams for NPs when considering these contributions (AIATnano) relative to a standard AIAT approach reveals significant qualitative and quantitative differences, which only become negligible for large systems. By constructing a size-dependent ΔGhyd(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).
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
J Phys Chem Lett
Año:
2024
Tipo del documento:
Article
País de afiliación:
España
Pais de publicación:
Estados Unidos