Molecular structures, conformations, and vibrational spectra of bicyclo[3.1.0]hexane and its oxygen analogues

Abstract

The molecular structures and ring-puckering potential energy profiles of bicyclo[3.1.0]hexane and its three oxygen analogues—6-oxabicyclo[3.1.0]hexane, 3-oxabicyclo[3.1.0]hexane, and 3,6-dioxa[3.1.0]hexane—have been reexamined using both ab initio (HF and MP2) and density functional theory (B3LYP) methods. The calculated structural parameters and ring-puckering potential profiles of those molecules have been compared to the previously reported microwave, electron diffraction, and far-infrared data. Our computational results show that the inclusion of electron correlation effects is crucial for the precise prediction of geometrical parameters of such bicyclic systems. The calculated ring-puckering potential energy profiles using the B3LYP method reproduce the experimental profiles more accurately than those predicted by MM3 force-field methods. Vibrational frequency calculations of 6-oxabicyclo[3.1.0]hexane have been also performed to compare with those measured from the infrared and Raman spectroscopy. Comparison of the calculated and experimental results indicates that the B3LYP method has led to the prediction of more accurate vibrational frequencies than the HF and MP2 methods.