Wertheim's association theory applied to one site patchy colloids: Beyond the single bonding condition

We apply Wertheim's theory to develop an equation of state for one site patchy colloids where the patch can bond multiple times. We allow for the possibility of ring formation without the introduction of empirical parameters and show that for moderate patch coverage the infinite series of chain graphs is well represented by the first two terms. The theory is found to be in excellent agreement with new NVT and NPT Monte Carlo simulations. The approach described here can easily be converted to the form of a density functional theory to describe inhomogeneous patchy colloid systems. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4751480]