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Thermally activated breakdown in a simple polymer model

We consider the thermally activated fragmentation of a homopolymer chain. In our simple model the dynamics of the intact chain is a Rouse one until a bond breaks and bond breakdown is considered as a first passage problem over a barrier to an absorbing boundary. Using the framework of the Wilemski-Fixman approximation we calculate activation times of individual bonds for free and grafted chains. We show that these times crucially depend on the length of the chain and the location of the bond yielding a minimum at the free chain ends. Theoretical findings are qualitatively confirmed by Brownian dynamics simulations.