Building and refining complete nanoparticle structures with total scattering data

Abstract

High-energy X-ray and spallation neutron total scattering data provide information about each pair of atoms in a nanoparticle sample, allowing for quantitative whole-particle structural modeling based on pair distribution function analysis. The realization of this capability has been hindered by a lack of versatile tools for describing complex finite structures. Here, the implementation of whole-particle refinement for complete nanoparticle systems is described within two programs,DISCUSandDIFFEV, and the diverse capabilities they present are demonstrated. The build-up of internal atomic structure (including defects, chemical ordering and other types of disorder), and nanoparticle size, shape and architecture (including core–shell structures, surface relaxation and ligand capping), are demonstrated using the programDISCUS. The structure refinement of a complete nanoparticle system (4 nm Au particles with organic capping ligands at the surface), based on neutron pair distribution function data, is demonstrated usingDIFFEV, a program using a differential evolutionary algorithm to generate parameter values. These methods are a valuable addition to other probes appropriate for nanomaterials, adaptable to a diverse and complex set of materials systems, and extendable to additional data-set types.