Canonical and microcanonical analysis of nongrafted homopolymer adsorption by an attractive substrate.

Using the off-lattice Monte Carlo simulation and replica-exchange method, we studied the behavior of nongrafted homopolymer adsorption by an attractive substrate from both the canonical and the microcanonical views. An adsorption transition is identified from the peak in canonical specific heat and compared with the conventional polymer adsorption with one end anchored on the surface of the substrate. Judging from the typical "backbending effect" and the negative specific heat in microcanonical ensemble, the transition is first-order-like when adsorption is relatively strong. However, it becomes second-order-like when the strength of adsorption becomes weak enough. Further study reveals that for a chain consisting of a limited number of monomers, the type of this transition becoming either first- or second-order-like depends not only on the interplay between monomer-monomer and monomer-substrate interaction, but also on the width of the gap in which it is confined.