Wertheim’s thermodynamic perturbation theory with double-bond association and its application to colloid–linker mixtures

We extend Wertheim’s thermodynamic perturbation theory to derive the association free energy of a multicomponent mixture for which double bonds can form between any two pairs molecules’ arbitrary number bonding sites. This generalization reduces in limiting cases prior theories that restrict at most one pair sites per molecule. apply new an associating colloidal particles (“colloids”) and flexible chain molecules (“linkers”). The linkers have functional end groups, each may bond several on colloids. Due their flexibility, significant fraction “loop” with both ends same colloid instead bridging different use show loops depends sensitively linker end-to-end distance relative bonding-site distance, suggests strategies mitigating loop formation otherwise hinder linker-mediated assembly.