The nature of the interactions of poly(methyl methacrylate) oligomers with an aluminum surface

Polymer–metal interfaces are of increasing technological importance in a variety of applications. These interfaces are characterized by specific interactions between functional groups of the organic polymer and the metallic substrate. In order to study the structure of these interfaces at the molecular level, the energetics of the segment–surface interactions must be well characterized. We have used density functional theory to investigate the interactions of poly(methyl methacrylate) (PMMA) oligomers with aluminum surfaces. The aluminum surface is represented by the simple jellium model. The energetics of the interactions between the organic molecules and the aluminum surface are calculated as a function of the orientation with respect to the surface of the organic molecule and various internal degrees of freedom. The computed energy hypersurfaces exhibit a rich structure characterized by several energy minima and barriers. Implications of such an energy hypersurface for the architecture of long chain molecules at the interface are discussed. The energy hypersurfaces also show that the rotational conformational statistics of PMMA interacting with an aluminum surface should be quite different from that of bulk PMMA. The reported energy hypersurfaces have been used to construct an empirical force‐field for future molecular simulations of long chains subject to the proper potentials.