PMID: 22587115May 17, 2012Paper

Mechanical desorption of a single chain: unusual aspects of phase coexistence at a first-order transition

Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics
A M SkvortsovKurt Binder

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 illus...Continue Reading

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Citations

Jun 2, 2014·The Journal of Chemical Physics·Leonid I KlushinKurt Binder
Sep 23, 2014·The Journal of Chemical Physics·Jutta Luettmer-Strathmann, Kurt Binder
Sep 28, 2017·Physical Review. E·Yacov Kantor, Mehran Kardar
Mar 22, 2013·The Journal of Chemical Physics·Himadri S Samanta, D Thirumalai
Aug 16, 2017·The Journal of Chemical Physics·Shuangshuang ZhangFriederike Schmid
Feb 26, 2021·Soft Matter·Geunho Noh, Panayotis Benetatos
Dec 18, 2013·Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics·G K Iliev, S G Whittington
Aug 15, 2015·Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics·G K Iliev, S G Whittington

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