  Motivated by often contradictory literature reports on size dependence of
surface energy of gold nanoparticles, we performed an atomistic study combining
molecular dynamics and \textit{ab initio} calculations. We show that in the
case of Au nanocubes, their surface energy converges to a value for $(0\,0\,1)$
facets of bulk crystals. A fast convergence to a single valued surface energy
is predicted also for nanosheres. In this case, however, the value of the
surface energy is larger than that of any low-index surface facet of bulk Au
crystal. This fact can be explained by the complex structure of the surface
with an extensive number of broken bonds due to edge and corner atoms. A
similar trend was obtained also for the case of cuboctahedron-shaped
nanoobjects. As the exact surface area of the nanoparticles is an ill-defined
quantity, we introduced the surface-induced excess energy and discussed this
quantity as a function of (i) number of atoms forming the nanoobject or (ii)
the nanoobject characteristic size. In case (i), a universal power-law
behaviour was obtained independent of the nanoparticle shape. Importantly, we
show that the size-dependence of the surface is hugely reduced is the surface
area correction due to the extend of electronic cloud is considered, a
phenomenon specifically important for small nanoparticles.

Materials Science