Zero-point vibrational effects on optical rotation

We investigate the effects of molecular vibrations on the optical rotation in two chiral molecules, methyloxirane and trans-2,3-dimethylthiirane. It is shown that the magnitude of zero-point vibrational corrections increases as the electronic contribution to the optical rotation increases. Vibrational effects thus appear to be important for an overall estimate of the molecular optical rotation, amounting to about 20-30% of the electronic counterpart. We also investigate the special case of chirality introduced in a molecule through isotopic substitution. In this case, the zero-point vibrational effects are the only source of optical activity, and we investigate the magnitude of these effects through calculations on mono-deuterated oxirane. (C) 2001 Elsevier Science B.V. All rights reserved.