Configurational entropy of adsorbed rigid rods: Theory and Monte Carlo simulations

Abstract

The configurational entropy of straight rigid rods of length k ( k -mers) adsorbed on square, honeycomb, and triangular lattices is studied by combining theory and Monte Carlo (MC) simulations in grand canonical and canonical ensembles. Three theoretical models to treat k -mer adsorption on two-dimensional lattices have been discussed: (i) the Flory–Huggins approximation and its modification to address linear adsorbates; (ii) the well-known Guggenheim–DiMarzio approximation; and (iii) a simple semi-empirical model obtained by combining exact one-dimensional calculations, its extension to higher dimensions and Guggenheim–DiMarzio approach. On the other hand, grand canonical and canonical MC calculations of the configurational entropy were obtained by using a thermodynamic integration technique. In the second case, the method relies upon the definition of an artificial Hamiltonian associated with the system of interest for which the entropy of a reference state can be exactly known. Thermodynamic integration is then applied to calculate the entropy in a given state of the system of interest. Comparisons between MC simulations and theoretical results were used to test the accuracy and reliability of the models studied.