Atomic Details of Interfacial Interaction in Gold Nanoparticles Supported on MgO(001).

Atomic-scale imaging using aberration-corrected scanning transmission electron microscopy reveals direct evidence for semicoherent interfacial epitaxy and coordinate-dependent surface contraction for the fcc (001) oriented Au nanoparticles (2-3 nm in diameter), suggesting that their interaction with the substrate is weaker than previously assumed. A significant change in interfacial separation distance from 2.47 ± 0.12 Å for the fcc (001) oriented Au nanoparticles to 3.07 ± 0.11 Å for the fcc (111) oriented Au nanoparticles has also been observed. These results are used to verify the atomistic models generated by the global optimization calculations, which shed further light on the intricate relation between the interfacial energy and the atomic structure of the nanoparticle and their combined effect on the inhomogeneous surface structural relaxation of supported nanoparticles.