Barrier crossing by a star polymer.
We analyze the dynamics of a star polymer of F arms trapped in a double well potential. Initially the molecule is confined to one of the minima and can cross over the barrier to the other side. We use the continuum version of the Rouse-Ham model and calculate the rate of crossing using the multidimensional approach due to Langer [Ann. Phys. (N.Y.) 54, 258 (1969)]. Finding the transition state for the process is shown to be equivalent to the solution of Newton's equations for F independent particles, moving in an inverted potential. For each star polymer, there is a critical barrier top curvature, below which the star crosses over in coiled conformation. The value of the critical curvature is determined by the first Rouse mode of the star. If the curvature is greater than this critical value, the saddle point for the crossing is a stretched conformation of the star. For the coiled transition state, the activation energy is proportional to the total arm length of the star. For the stretched transition state, as one increases the length of an arm of the star, the activation energy at first increases and then decreases. This results from the fact that in the stretched state, only one arm of the polymer is stretched across the top of the barrier, while others need not be. We calculate the rate by expanding the energy around the saddle up to second order in the fluctuations. As we use the continuum model, there are infinite modes for the polymer and, consequently, the prefactor has infinite products. We show that these infinite products can be reduced to a simple expression, and evaluated easily. However, the rate diverges near NTc due to the multifurcation, which results in more than one unstable mode. The cure for this divergence is to keep terms up to fourth order in the expansion of energy for these modes. Performing this, we have calculated the rate as a function of the length of the star. It is found that the rate has a nonmonotonic dependence on the length, suggesting that longer stars may actually cross over the barrier faster.
Debnath
Ananya
A
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India.
Sebastian
K L
KL