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Abstract: In detailed microcanonical analyses of densities of states obtained byextensive multicanonical Monte Carlo computer simulations, we investigate thecaloric properties of conformational transitions adsorbing polymers experiencenear attractive substrates. For short chains and strong surface attraction, themicrocanonical entropy turns out to be a convex function of energy in thetransition regime, indicating that surface-entropic effects are relevant.Albeit known to be a continuous transition in the thermodynamic limit ofinfinitely long chains, the adsorption transition of nongrafted finite-lengthpolymers thus exhibits a clear signature of a first-order-like transition, withcoexisting phases of adsorbed and desorbed conformations. Another remarkableconsequence of the convexity of the microcanonical entropy is that thetransition is accompanied by a decrease of the microcanonical temperature withincreasing energy. Since this is a characteristic physical effect it might notbe ignored in analyses of cooperative macrostate transitions in finite systems.



Author: Monika Möddel, Wolfhard Janke, Michael Bachmann

Source: https://arxiv.org/







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