Polymer clay nanocomposites (PCN) show enhanced mechanical, thermal, liquid or gas barrier properties in comparison to pure polymer. However, the mechanisms for enhancement of these physical properties of PCN are not well understood. This knowledge is important for tailoring the properties of PCN to desired specifications. Our earlier study showed that organic modifiers have significant influence on the crystallinity and nanomechanical properties of PCN. For quantitative evaluation of the influence of organic modifiers on the crystallinity and nanomechanical properties of PCN, molecular models of three intercalated PCNs containing same polymer and clay but with three different organic modifiers are constructed in this work. Using molecular dynamics simulations, the interaction energies among the different constituents of PCNs are evaluated. This study reveals that the interactions between polymer, organic modifiers, and intercalated clay are critical factors in controlling the crystallinity and enhancement of nanomechanical properties of PCN. We have described the possible mechanisms leading to change in crystallinity and nanomechanical properties. (c) 2007 Wiley Periodicals, Inc.