Study of thermodynamic parameters in amphiphilic systems by lattice Monte Carlo: effect of tails and heads

Abstract

Results from three-dimensional lattice Monte Carlo simulations of amphiphile–solvent mixtures are presented. The chemical potential is derived from the monomer distribution in different clusters rather than using a Widom particle insertion approach. The effect of tail and head characteristics on the non-ideality of these systems, aggregation number, and premicellar phenomena is considered. The aggregation number and CMC behavior of the simulated amphiphilic systems are compared with existing experimental results for non-ionic amphiphiles. Two kinds of polydispersity changing with total concentration of surfactants are observed which are related to phase transition phenomena. Shape variations in clusters are studied by calculating the eigenvalues of the gyration matrix; it is shown that large clusters are non-spherical. With the Maclaurin’s expansion of activity coefficient into volume fraction, the distribution of excess chemical potential with changing aggregation number is considered. Study of the degree of non-ideality of these amphiphiles reveals that asymmetric amphiphiles are characterized by greater non-ideality than symmetric amphiphiles. Goldstein’s parameters are calculated taking non-ideality into consideration. The difference between the phenomenological model and the simulation data is investigated.