Ring strain

An energetic penalty from bond angles, torsions or nonbonded contacts forced away from favourable values by ring closure.

Torsional strain is an increase in the energy of a molecule associated with an unfavourable torsion angle, relative to a stated reference conformation. Rotation about a bond can change the relative orientations of substituents without changing which atoms are bonded. The IUPAC definition of strain explicitly includes unfavourable dihedral angles alongside bond-length and bond-angle distortions.^[ref]

Consider ethane viewed along its central carbon–carbon bond. An eclipsed conformation aligns projected carbon–hydrogen bonds, whereas a staggered conformation places them between one another. An idealized threefold potential energy model iswith $\varphi =0$ chosen eclipsed. It gives $V(0)=V_3$ and $V(\pi /3)=0$: a finite rotational barrier separates equivalent minima. The model is a teaching parametrization; $V_3$ must be obtained independently rather than read from the drawing.

The 1937 paper by J. D. Kemp and K. S. Pitzer explicitly connected the entropy of ethane and the third law of thermodynamics with hindered methyl-group rotation.^[ref] This historical connection shows why internal rotation is a measurable molecular degree of freedom, not simply unrestricted motion around a single bond. In a ring, geometric closure can restrict accessible torsion angles; ring strain can therefore include torsional strain as well as other contributions. Assigning a separate torsional energy is model-dependent, rather than a complete account of every electronic interaction.