International Journal of Quantum Chemistry

Molecular dynamics simulations of n‐Alkane melts confined between solid surfaces

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Molecular dynamics simulations of polyethylene chains (CnH2n+2 for n = 13, 16, 28, 60) have been carried out to investigate both equilibrium and dynamic properties of polymer melts confined between flat solid surfaces. We observe an oscillatory monomer density in the direction normal to the solid surfaces, which depends on the size of the monomers (i.e., on the volume density of the system). The packing manner of monomer segments, segment orientation, and local conformations of chains are found to be independent of chain length. In addition, preferential interfacial adsorption of chain ends is observed. The chains are flattened close to the surface and many molecules assume essentially two‐dimensional train configurations even in the case of C60H122 melts. The apparent self‐diffusivities of the centers of mass of the molecules depend on their distance from a surface. Molecules adjacent to a surface exhibit a reduced mobility perpendicular to the surface and an increased one parallel to it. The self‐diffusion constant parallel to a surface depends strongly on the size of the monomers. An increase of the united atom diameter by 10% reduces the diffusion constant by a factor of three, in good agreement with the experimental value. © 1994 John Wiley & Sons, Inc. Copyright © 1994 John Wiley & Sons, Inc.