Abstract
Semiflexible polymers bound to planar substrates by a short-range surface potential are studied by Molecular Dynamics simulations to clarify the extent to which these chain molecules can be considered as strictly two-dimensional. Applying a coarse-grained bead-spring model, the chain length N and stiffness κ as well as the strength of the adsorption potential ϵ w a l l are varied over a wide range. The excluded-volume (EV) interactions inherent in this model can also be "switched off" to provide a discretized version of the Kratky-Porod wormlike chain model. We study both local order parameters (fraction f of monomers within the range of the potential, bond-orientational order parameter η ) and the mean square gyration radius parallel, 〈 R g 2 〉 | | , and perpendicular, 〈 R g 2 〉 ⟂ , to the wall. While for strongly adsorbed chains EV has negligible effect on f and η , we find that 〈 R g 2 〉 | | is strongly affected when the chain contour length exceeds the persistence length. Monomer coordinates in perpendicular (⟂) direction are correlated over the scale of the deflection length which is estimated. It is found that f , η , and 〈 R g 2 〉 ⟂ converge to their asymptotic values with 1 / N corrections. For both weakly and strongly adsorbed chains, the distribution functions of "loops", "trains", and "tails" are analyzed. Some consequences pertaining to the analysis of experiments on adsorbed semiflexible polymers are pointed out.