The role of bond tangency and bond gap in hard sphere crystallization of chains.

We report results from Monte Carlo simulations on dense packings of linear, freely-jointed chains of hard spheres of uniform size. In contrast to our past studies where bonded spheres along the chain backbone were tangent, in the present work a finite tolerance in the bond is allowed. Bond lengths are allowed to fluctuate in the interval [σ, σ + dl], where σ is the sphere diameter. We find that bond tolerance affects the phase behaviour of hard-sphere chains, especially in the close vicinity of the melting transition. First, a critical dl(crit) exists marking the threshold for crystallization, whose value decreases with increasing volume fraction. Second, bond gaps enhance the onset of phase transition by accelerating crystal nucleation and growth. Finally, bond tolerance has an effect on crystal morphologies: in the tangent limit the majority of structures correspond to stack-faulted random hexagonal close packing (rhcp). However, as bond tolerance increases a wealth of diverse structures can be observed: from single fcc (or hcp) crystallites to random hcp/fcc stackings with multiple directions. By extending the simulations over trillions of MC steps (10(12)) we are able to observe crystal-crystal transitions and perfection even for entangled polymer chains in accordance to the Ostwald's rule of stages in crystal polymorphism. Through simple geometric arguments we explain how the presence of rigid or flexible constraints affects crystallization in general atomic and particulate systems. Based on the present results, it can be concluded that proper tuning of bond gaps and of the connectivity network can be a controlling factor for the phase behaviour of model, polymer-based colloidal and granular systems.