We demonstrate that the experimentally observed sign change of the optical rotation of (S)-methyloxirane when going from 589 nm to 355 nm is due to zero-point vibrational corrections. The previous agreement between DFT/B3LYP calculations at a wavelength of 355 nm is shown to be fortuitous due to a too low excitation energy predicted by DFT/B3LYP. Excellent agreement between theory and experiment is obtained when CC3 equilibrium optical rotations are combined with the zeropoint vibrational contributions calculated in this communication.

The importance of molecular vibration: the sign change of the optical rotationof methyloxirane

ZANASI, Riccardo
2005

Abstract

We demonstrate that the experimentally observed sign change of the optical rotation of (S)-methyloxirane when going from 589 nm to 355 nm is due to zero-point vibrational corrections. The previous agreement between DFT/B3LYP calculations at a wavelength of 355 nm is shown to be fortuitous due to a too low excitation energy predicted by DFT/B3LYP. Excellent agreement between theory and experiment is obtained when CC3 equilibrium optical rotations are combined with the zeropoint vibrational contributions calculated in this communication.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11386/1058337
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