Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

Monte Carlo simulations of chain conformations in restricted spherical volumes with an increasing radius were performed on a tetrahedral lattice (ca 2 700 to 9 200 lattice sites) at relatively high densities of the occupied lattice sites. A simultaneous self-avoiding walk together with the equilibration algorithm similar to that of Siepmann and Frenkel were used to create the equilibrated multi-chain conformations. (a) A series of simulations was carried out for a constant average segment density, <g_S> = 0.52, together with the three values of the radius of the sphere, R = 10 l, 12.5 l and 15 l (l is the lattice distance), and various numbers of chains, N ∈ <15, 86>, and chain lengths, L ∈ <31, 163>. The results give information on the system behavior and on the effects of: (i) multi-chain conformational correlations, which depend both on N and L, (ii) the L-dependent chain flexibility, and (iii) R-dependent external geometrical constraints. Another two series of data: (b) for a constant average segment density, <g_S> = 0.36, a constant N = 21, and L proportional to R³, and (c) for <g_S> = 0.36, L = 47 and N proportional to R³, are shown to give a supplementary detailed information on conformational behavior of individual chains. Various physical quantities (e.g. the densities of chain free ends, g_F(r), or distributions of the tethered end-to-the free end distances, ρ_TF(r_TF), etc.) were calculated in the course of computer simulations and their shapes and physical significance is discussed with respect to the changing values of N, L and R.