We provide a study
of the assembly of single-component nanocrystals
(NCs) (nanoparticles) capped with polystyrene by solvent evaporation.
We investigate regimes from the colloidal R
G/R
c ≪ 1, with R
c (core radius) and R
G (ligand
gyration radius), to polymer limit R
G/R
c ≫ 1. We show that for increasing chain
length, there is the emergence of a “cascade effect,”
that is, an abrupt drop in internal energy with the resulting potential
of mean force dominated by configurations wherein the chains bend
over the core in order to maximize contacts with the other NC, which
accounts for the large magnitude of the many-body effects in the superlattice
free energy. Interestingly, the orbifold topological model, that successfully
characterizes the NC interaction in the colloidal limit, quantitatively
describes the polymer limit as well. Our results establish that bcc
is the equilibrium phase. Implications for recent and future experiments
are discussed.
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