Semi-flexible hydrogen-bonded and non-hydrogen bonded lattice polymers

Abstract

We investigate the addition of stiffness to the lattice model of hydrogen-bonded polymers in two and three dimensions. We find that, in contrast to polymers that interact via a homogeneous short-range interaction, the collapse transition is unchanged by any amount of stiffness: this supports the physical argument that hydrogen bonding already introduces an effective stiffness. Contrary to possible physical arguments, favouring bends in the polymer does not return the model’s behaviour to that comparable with the semi-flexible homogeneous interaction model, where the canonical θ -point occurs for a range of parameter values. In fact, for sufficiently large bending energies the crystal phase disappears altogether, and no phase transition of any type occurs. We also compare the order-disorder transition from the globule phase to crystalline phase in the semi-flexible homogeneous interaction model to that for the fully-flexible hybrid model with both hydrogen and non-hydrogen like interactions. We show that these phase transitions are of the same type and are a novel polymer critical phenomena in two dimensions. That is, it is confirmed that in two dimensions this transition is second-order, unlike in three dimensions where it is known to be first order. We also estimate the crossover exponent in two dimensions and show that there is a divergent specific heat, finding ϕ = 0.7 ( 1 ) or equivalently α = 0.6 ( 2 ) . This is therefore different from the θ transition, for which α = − 1 / 3 .