Polymer collapse and crystallization in bond fluctuation models

Abstract: While the $\Theta$-collapse of single long polymers in bad solvents is usually a continuous (tri-critical) phase transition, there are exceptions where it is preempted by a discontinuous crystallization (liquid $\leftrightarrow$ solid) transition. For a version of the bond-fluctuation model (a model where monomers are represented as $2\times 2\times 2$ cubes, and bonds can have lengths between 2 and $\sqrt{10}$) it was recently shown by F. Rampf {\it et al.} that there exist distinct collapse and crystallization transitions for long but {\it finite} chains. But as the chain length goes to infinity, both transition temperatures converge to the same $T^*$, i.e. infinitely long polymers collapse immediately into a solid state. We explain this by the observation that polymers crystallize in the Rampf {\it et al.} model into a non-trivial cubic crystal structure (the A15' orCr$_3$Si' Frank-Kasper structure) which has many degenerate ground states and, as a consequence, Bloch walls. If one controlls the polymer growth such that only one ground state is populated and Bloch walls are completely avoided, the liquid-solid transition is a smooth cross-over without any sharp transition at all.