2007
DOI: 10.1063/1.2406075
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Negative compressibility and nonequivalence of two statistical ensembles in the escape transition of a polymer chain

Abstract: An end-tethered polymer chain compressed between two pistons undergoes an abrupt transition from a confined coil state to an inhomogeneous flowerlike conformation partially escaped from the gap. This phase transition is first order in the thermodynamic limit of infinitely long chains. A rigorous analytical theory is presented for a Gaussian chain in two ensembles: ͑a͒ the H-ensemble, in which the distance H between the pistons plays the role of the independent control parameter, and ͑b͒ the conjugate f-ensembl… Show more

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Cited by 23 publications
(19 citation statements)
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“…The same technique has also proved the presense of NLC in methanol monohydrate (Fortes et al, 2011). Other materials have been shown to have NLC triggered by a pressure induced phase transition, molecular dynamic simulations show that hydrocarbon chains will experience a very pronounced phase change under high hydrostatic loading that leads to the chains suddenly becoming aligned thus causing an expansion on a particular axis (Skvortsov et al, 2007). Paratellurite was shown to exhibit NLC (Skelton et al, 1976) due to a phase transition induced by increased pressure where the symmetry changes from a tetragonal to an orthorhombic structure at 8kbar.…”
Section: Introductionmentioning
confidence: 99%
“…The same technique has also proved the presense of NLC in methanol monohydrate (Fortes et al, 2011). Other materials have been shown to have NLC triggered by a pressure induced phase transition, molecular dynamic simulations show that hydrocarbon chains will experience a very pronounced phase change under high hydrostatic loading that leads to the chains suddenly becoming aligned thus causing an expansion on a particular axis (Skvortsov et al, 2007). Paratellurite was shown to exhibit NLC (Skelton et al, 1976) due to a phase transition induced by increased pressure where the symmetry changes from a tetragonal to an orthorhombic structure at 8kbar.…”
Section: Introductionmentioning
confidence: 99%
“…Although the equivalence of the Gibbs and Helmholtz statistical ensemble has been proved for a large class of systems (namely, single flexible polymer chains without confinement effects and with a continuous pairing interaction potential between neighboring monomers [86][87][88][89][90][91]), interestingly, it cannot be assumed for other structures. Indeed, other classes of problems, e.g., concerning the escape of a polymer confined between two surfaces and the desorption of a polymer initially tethered onto a surface, exhibit an unusual nonequivalence between the defined statistical ensembles [113][114][115][116][117][118]. In particular, in Refs.…”
Section: Discussionmentioning
confidence: 99%
“…In particular, in Refs. [113,114] an end-tethered polymer chain compressed between two pistons is considered and shows nonequivalence of the ensembles and a phase transition corresponding to the escape from the gap between the pistons. Reference [115] deals with the desorption of a single chain from a substrate without excluded volume interactions: also in this case the equivalence of the ensembles and the emergence of a phase transition are thoroughly discussed.…”
Section: Discussionmentioning
confidence: 99%
“…However, it is noteworthy to mention that some particular cases on non-equivalence between dual canonical ensembles have been recently discussed for confined polymer chains. [90][91][92]…”
Section: Thermodynamics Of Chains With Conformational Transitionsmentioning
confidence: 99%