Replica Ornstein-Zernike theory of adsorption in a templated porous material: Interaction site systems

Molecular templating offers the possibility of porous materials whose selectivity rivals the molecular recognition observed in nature. The design of templated materials requires a molecular understanding of the templating effect on the material structure and performance. We present here a theoretical description of adsorption in a model templated porous material. Our model material is a quenched, equilibrated mixture of template and matrix molecular species where the template component has been subsequently removed. We propose a set of site-site [i.e., reference interaction site model (RISM)] replica Ornstein-Zernike equations relating the correlation functions of template, matrix, and adsorbing fluid molecules. To test this approach, we focus here on systems interacting via hard-sphere site-site potentials and employ a Percus-Yevick closure. We consider chain and cluster species composed of up to five spheres and observe a range of effects associated with template structure, including higher affinity toward, and enhanced templating by, compact cluster molecules. We assess these effects by grand canonical Monte Carlo simulation and discuss their implication to the design of templated molecular recognition materials.