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We show that the structural properties and phase behavior of a self-avoidingpolymer chain on adhesive substrate, subject to pulling at the chain end, canbe obtained by means of a Grand Canonical Ensemble (GCE) approach. We deriveanalytical expressions for the mean length of the basic structural units ofadsorbed polymer, such as loops and tails, in terms of the adhesive potentialand detachment force, and determine values of the universal exponents whichgovern their probability distributions. Most notably, the hithertocontroversial value of the critical adsorption exponent $\phi$ is found todepend essentially on the interaction between different loops. The chaindetachment transition turns out to be of the first order, albeit dichotomic,i.e., no coexistence of different phase states exists. These novel theoreticalpredictions and the suggested phase diagram of the adsorption-desorptiontransformation under external pulling force are verified by means of extensiveMonte Carlo simulations.

Polymer desorption under pulling: a novel dichotomic phase transition