In order to examine the correlation between stiffness and excluded‐volume effects in polymer chains, polymethylene‐like rotational isomeric state chains with excluded volume are simulated and their mean‐square radii of gyration are evaluated by Monte Carlo methods. The present results and also experimental data for ordinary flexible chains may well be explained by the Kratky–Porod worm‐like chain, or more generally the helical worm‐like chain, with the excluded‐volume effects incorporated in the Yamakawa–Stockmayer scheme. For typical stiff chains with excluded volume, however, there is clear disagreement between their theory and experiment, and the problem remains unsolved.
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1985
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