Ab-Initio molecular geometry and normal coordinate analysis of pyrrolidine molecule

Abstract

The molecular geometry of pyrrolidine was quantum mechanically calculated using the split valence 6-31G** basis set. Electron correlation energy has been computed employing MP2 method. The molecule showed an envelope form puckered structure with inter-plane angle of 36.4° and has a total energy of −132976.80 kcal mol −1 of which a −464.86 kcal mol −1 electron correlation energy. The twist form of the molecule showed a twist angle of 10.2° from planarity and has a total energy of −132976.05 kcal mol −1 involving −464.097 kcal mol −1 electron correlation energy. The normal coordinates of the molecule were theoretically analyzed on the basis of the Cs point symmetry of the envelope form. Using initial set of force constants obtained from the ab-initio calculations the fundamental vibrational frequencies were computed. The IR and laser Raman spectra of Pyrrolidine molecules were measured. All the observed vibrational bands including combination bands and overtones were assigned to normal modes with the aid of the potential energy distribution values obtained from normal coordinate calculations. The molecular force field was obtained by refining the initial set of force constants using the least square fit method. The molecular force field was determined by refining the initial set of force constants using the least square fit method instead of using the less accurate scaling factor methods. The determined molecular force field has produced simulated frequencies best match to the observed values. The low frequency molecular out-of-plane deformation modes were observed in both infrared and Raman spectra at 298 and 163 cm −1. The barrier of ring twisting estimated from the observed ring out-of-plane vibrational mode at 163 cm −1 was found 3.1 kcal mol −1.