We investigate the effects of the range of adsorption potential on the equilibrium behavior of a single polymer chain end-attached to a solid surface. The exact analytical theory for ideal lattice chains interacting with a planar surface via a box potential of depth $U$ and width $W$ is presented and compared to continuum model results and to Monte Carlo (MC) simulations using the pruned-enriched Rosenbluth method for self-avoiding chains on a simple cubic lattice. We show that the critical value $U_c$ corresponding to the adsorption transition scales as $W^{-1/\nu }$, where the exponent $\nu =1/2$ for ideal chains and $\nu \approx 3/5$ for self-avoiding walks. Lattice corrections for finite $W$ are incorporated in the analytical prediction of the ideal chain theory $U_c\approx \left(\frac{{\pi }^2}{24}\right){(W+1/2)}^{-2}$ and in the best-fit equation for the MC simulation data $U_c=0.585{(W+1/2)}^{-5/3}$. Tail, loop, and train distributions at the critical point are evaluated by MC simulations for $1\le W\le 10$ and compared to analytical results for ideal chains and with scaling theory predictions. The behavior of a self-avoiding chain is remarkably close to that of an ideal chain in several aspects. We demonstrate that the bound fraction $\theta$ and the related properties of finite ideal and self-avoiding chains can be presented in a universal reduced form: $\theta (N,U,W)=\theta (N{U}_c,U/U_c)$. By utilizing precise estimations of the critical points we investigate the chain length dependence of the ratio of the normal and lateral components of the gyration radius. Contrary to common expectations this ratio attains a limiting universal value $\langle R_{g\perp }^2\rangle /\langle R_{g\parallel }^2\rangle =0.320\pm 0.003$ only at $N\sim 5000$. Finite-$N$ corrections for this ratio turn out to be of the opposite sign for $W=1$ and for $W\ge 2$. We also study the $N$ dependence of the apparent crossover exponent ${\varphi }_{\mathrm{eff}}\left(N\right)$. Strong corrections to scaling of order $N^{-0.5}$ are observed, and the extrapolated value $\varphi =0.483\pm 0.003$ is found for all values of $W$. The strong correction to scaling effects found here explain why for smaller values of $N$, as used in most previous work, misleadingly large values of ${\varphi }_{\mathrm{eff}}\left(N\right)$ were identified as the asymptotic value for the crossover exponent.

• Received 23 December 2012

DOI:https://doi.org/10.1103/PhysRevE.87.022604