Role of internal chain dynamics on the rupture kinetic of adhesive contacts.

We study the forced rupture of adhesive contacts between monomers that are not covalently linked in a Rouse chain. When the applied force (f) to the chain end is less than the critical force for rupture (f{c}), the reversible rupture process is coupled to the internal Rouse modes. If f/f{c}>1 the rupture is irreversible. In both limits, the nonexponential distribution of contact lifetimes, which depends sensitively on the location of the contact, follows the double-exponential (Gumbel) distribution. When two contacts are well separated along the chain, the rate limiting step in the sequential rupture kinetics is the disruption of the contact that is in the chain interior. If the two contacts are close to each other, they cooperate to sustain the stress, which results in an "all-or-none" transition.