Compressive axial forces in long-chain molecules due to excluded-volume effects

Publisher Website
Google Scholar
Abstract
The force length relation f(r) for a freely jointed chain with excluded volume is studied by computer simulation. For the case of the strain ensemble (r fixed and f fluctuates) it is found that excluded‐volume effects cause f to be compressive (fr, in contrast to the stress ensemble (f fixed and r fluctuates) which leads to f≥0 for all r. The computation procedure also provides the separate covalent and noncovalent contributions to f and the average molecular shape; these provide additional physical insight.