Excluded volume

The concept of excluded volume was introduced by Werner Kuhn in 1934 and applied to polymer molecules shortly thereafter by Paul Flory.

The distance of closest approach of hard ellipses and their excluded area has been recently considered.

It also led to the concept of the theta point, the set of conditions at which an experiment can be conducted that causes the excluded volume effect to be neutralized.

[4] The long-range interactions arising from excluded volume are eliminated, allowing the experimenter to more easily measure short-range features such as structural geometry, bond rotation potentials, and steric interactions between near-neighboring groups.

Flory correctly identified that the chain dimension in polymer melts would have the size computed for a chain in ideal solution if excluded volume interactions were neutralized by experimenting at the theta point.