title: Mechanical desorption of a single chain: unusual aspects of phase coexistence at a first-order transition.
abstract: The phase transition occurring when a single polymer chain adsorbed at a planar solid surface is mechanically desorbed is analyzed in two statistical ensembles. In the force ensemble, a constant force applied to the nongrafted end of the chain (that is grafted at its other end) is used as a given external control variable. In the z-ensemble, the displacement z of this nongrafted end from the surface is taken as the externally controlled variable. Basic thermodynamic parameters, such as the adsorption energy, exhibit a very different behavior as a function of these control parameters. In the thermodynamic limit of infinite chain length the desorption transition with the force as a control parameter clearly is discontinuous, while in the z-ensemble continuous variations are found. However, one should not be misled by a too-naive application of the Ehrenfest criterion to consider the transition as a continuous transition: rather, one traverses a two-phase coexistence region, where part of the chain is still adsorbed and the other part desorbed and stretched. Similarities with and differences from two-phase coexistence at vapor-liquid transitions are pointed out. The rounding of the singularities due to finite chain length is illustrated by exact calculations for the nonreversal random walk model on the simple cubic lattice. A new concept of local order parameter profiles for the description of the mechanical desorption of adsorbed polymers is suggested. This concept give evidence for both the existence of two-phase coexistence within single polymer chains for this transition and the anomalous character of this two-phase coexistence. Consequences for the proper interpretation of experiments performed in different ensembles are briefly mentioned.
authors.affiliation: Chemical-Pharmaceutical Academy, St. Petersburg, Russia. astarling@yandex.ru
authors.forename: Alexander M
authors.initials: AM
authors.lastname: Skvortsov
authors.forename: Leonid I
authors.initials: LI
authors.lastname: Klushin
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Polotsky
authors.forename: Kurt
authors.initials: K
authors.lastname: Binder
mesh_terms: D000268:Adhesiveness; D000327:Adsorption; D003198:Computer Simulation; D004735:Energy Transfer; D008956:Models, Chemical; D008958:Models, Molecular; D044367:Phase Transition; D011108:Polymers / Q000737:chemistry*; D013499:Surface Properties; D013816:Thermodynamics
chemical_list: D011108:Polymers