Publicado in Henry Rzepa's Blog

I wrote in an earlier post how Pauling’s Nobel prize-winning suggestion in February 1951 of a (left-handed) α-helical structure for proteins[cite]10.1073/pnas.37.4.205[/cite] was based on the wrong absolute configuration of the amino acids (hence his helix should really have been the right-handed enantiomer). This was most famously established a few months later by Bijvoet’s[cite]10.1038/168271a0[/cite] definitive crystallographic

References

Physical and Theoretical ChemistryGeneral Physics and Astronomy
Inglés

The Absolute Configuration of Optically Active Molecules

Publicado in The Journal of Chemical Physics
Autores William W. Wood, Wildon Fickett, John G. Kirkwood

The problem of the absolute configuration of optically active molecules is investigated with the aid of the Kirkwood theory of optical rotatory power. Absolute configurations are assigned to the enantiomorphs of 2,3-epoxybutane and 1,2-dichloropropane. The assignments are consistent with the established experimental configurational relationships between these compounds. The Fischer convention is confirmed as a structurally correct representation of absolute configuration. The magnitudes of the calculated rotations of the compounds are in reasonably good agreement with experiment. The theory accounts satisfactorily for the effect of temperature and solvent on the optical rotation of 1,2-dichloropropane.

Physical and Theoretical ChemistryGeneral Physics and Astronomy
Inglés

On the Theory of Optical Rotatory Power

Publicado in The Journal of Chemical Physics
Autor John G. Kirkwood

The Born theory of optical activity in quantum-mechanical form is simplified with the aid of certain approximations. It leads to a simple expression for the rotatory parameter of an active molecule in terms of the geometrical configuration and the polarizability tensors of its constituent groups. Optical anisotropy of the component groups and inhibited internal rotation are found to play an important role in determining rotatory power. The proposed theory has points of similarity both with the polarizability theories of Gray, de Mallemann, and Boys and also with Kuhn's specialization of Born's classical theory of optical activity. To illustrate its use, the absolute configuration and the specific rotation of d-secondary butyl alcohol are calculated.