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The effect of excluded volume on the coil size of dilute linear polymers was investigated by off-lattice Monte Carlo simulations. The radius of gyration Rg was evaluated for a wide range of chain lengths at several temperatures and at the athermal condition. The θ temperature and the corresponding θ chain dimensions were established for the system, and the dependence of the size expansion factor, αs = Rg/(Rg)θ, on chain length N and temperature T was examined. For long chains and at high temperatures, αs is a function of N/Ns⧧ alone, where the length scale Ns⧧ depends only on T. The form of this simulations-based master function compares favorably with αs(M/Ms⧧), an experimental master curve for linear polymers in good solvents, where Ms⧧ depends only on polymer−solvent system. Comparisons when Ns⧧(T) and Ms⧧(system) are reduced to common units, numbers of Kuhn steps, strongly indicate that coil expansion in even the best of good solvents is small relative to that expected for truly athermal solutions. An...

Excluded-Volume Effects in Polymer Solutions. 2. Comparison of Experimental Results with Numerical Simulation Data