The ideal polymer chain near planar hard wall beyond the Dirichlet boundary conditions |
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Authors: | I Y Erukhimovich A Johner J F Joanny |
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Institution: | (1) Moscow State University, 119992 Moscow, Russia;(2) Institute Charles Sadron, 6 rue Boussingault, 67083 Strasbourg Cedex, France;(3) Physicochimie Curie, Institut Curie Section Recherche, 26 rue d’Ulm, 75248 Paris, France |
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Abstract: | We present a new ab initio approach to describe the statistical behavior of long ideal polymer chains near a plane hard wall. Forbidding the solid half-space
to the polymer explicitly (by the use of Mayer functions) without any other requirement, we derive and solve an exact integral
equation for the partition function G
D(r,r′, N) of the ideal chain consisting of N bonds with the ends fixed at the points r and r′ . The expression for G(r,r′, s) is found to be the sum of the commonly accepted Dirichlet result G
D(r,r′, N) = G
0(r,r′, N) - G
0(r,r”, N) , where r” is the mirror image of r′ , and a correction. Even though the correction is small for long chains, it provides a non-zero value of the monomer density
at the very wall for finite chains, which is consistent with the pressure balance through the depletion layer (so-called wall
or contact theorem). A significant correction to the density profile (of magnitude 1/is obtained away from the wall within one coil radius. Implications of the presented approach for other polymer-colloid problems
are discussed. |
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Keywords: | PACS" target="_blank">PACS 82 35 Gh Polymers on surfaces adhesion 61 25 he Polymer solutions 05 70 Np Interface and surface thermodynamics |
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