Ab initio study of the pseudorotation in 1,3-dioxolane

Equilibrium molecular structures, vibrational wavenumbers, and the potential energy surface for the twisting and wagging large amplitude motions of the ring in 1,3-dioxolane have been calculated at the second-order Moller-Plesset (MP2) level of perturbation theory using an extended basis set up to 6-311 + G(3df,3p). The existence of four energy minima has been confirmed by the calculations. Furthermore, a dynamical pseudorotation model has been derived from the calculated four local minima that are separated by low barriers, and the potential energy surface. The results of the present theoretical study have been critically compared with those of previous experimental studies as well as with previous lower level theoretical studies. (C) 2001 Elsevier Science B.V. All rights reserved.