Periodic copolymers at selective interfaces: a large deviations approach

DOI10.1214/105051604000000800MaRDI QIDQ1774204zbMATH OpenOpenAlexFDO

Authors Erwin Bolthausen, Giambattista Giacomin

Publication date 29 April 2005

Published in The Annals of Applied Probability (Search for Journal in Brave)

Full work available at URL https://arxiv.org/abs/math/0503523

Donsker-Varadhan theory.energy-entropy competition localization-delocalization transition random walk

Large deviations (60F10) Interacting random processes; statistical mechanics type models; percolation theory (60K35) Random walks, random surfaces, lattice animals, etc. in equilibrium statistical mechanics (82B41)

Abstract: We analyze a (1+1)-dimension directed random walk model of a polymer dipped in a medium constituted by two immiscible solvents separated by a flat interface. The polymer chain is heterogeneous in the sense that a single monomer may energetically favor one or the other solvent. We focus on the case in which the polymer types are periodically distributed along the chain or, in other words, the polymer is constituted of identical stretches of fixed length. The phenomenon that one wants to analyze is the localization at the interface: energetically favored configurations place most of the monomers in the preferred solvent and this can be done only if the polymer sticks close to the interface. We investigate, by means of large deviations, the energy-entropy competition that may lead, according to the value of the parameters (the strength of the coupling between monomers and solvents and an asymmetry parameter), to localization. We express the free energy of the system in terms of a variational formula that we can solve. We then use the result to analyze the phase diagram.

Review text

\textit{E. Bolthausen} and \textit{F. den Hollander} [Ann. Probab. 25, No. 3, 1334--1366 (1997; Zbl 0885.60022)], considered a model for a heterogeneous polymer consisting of hydrophobic and hydrophylic monomers near an oil-water interface. Each \(N\)-step path of \(S=(S_x; x\in \mathbb N )\), a simple symmetric random walk on \(\mathbb Z\) starting at 0, is weighted by the Hamiltonian \[ H_N (S)= \lambda\sum_{x=1}^N (\omega_x +h)\Delta_x, \] where \(\Delta_x=\text{ sign} (S_x)\) if \(S_x\neq 0\) and \(\Delta_x=\text{ sign} (S_{x-1})\) if \(S_x= 0\). \(\lambda\geq 0\) is the coupling constant which plays the role of inverse temperature, \(h\geq 0\) is a parameter, and \(\omega =(\omega_x)\) is an i.i.d. sequence of random variables taking values \(\pm 1\) with probability \(1/2\). They showed that there is a critical curve \(\lambda\mapsto h_c(\lambda)\) where phase transition occurs between localized and delocalized behavior. In this paper, the paths of \(S\) are weighted by the same Hamitonian, \(H_N\), but the basic assumption is that \(\omega\) is a fixed nontrivial centered and periodic sequence of \(\pm 1\)'s. The first result is an expression of the free energy in terms of the empirical measure of a Markov chain constructed from the return times to 0 of \(S\). A second expression of the free energy is given as the supremum of a variational problem which evaluates the competition between the energy and the entropy of the Markov chain. To prove this, one first shows, as is \textit{E. Bolthausen} [Stochastic Processes Appl. 25, 95--108 (1987; Zbl 0625.60026)], that the empirical measure of the Markov chain verifies a full large deviation principle with rate functional given by the entropy. This leads to a fairly explicit formula for the free energy in terms of the Perron-Frobenius maximal eigenvalue. The existence of a critical curve and its precise asymptotic behavior at small and large values of \(\lambda\) then follows.

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