Ab-initio molecular geometry and normal coordinate analysis of tetrahydrothiophene molecule

Abstract

The molecular geometry of tetrahydrothiophene (THT) was quantum mechanically calculated using the split valence 6–31G** basis set. Electron correlation energy has been computed employing MP2 method. The molecule showed a twist form puckered structure with a twist torsion angle of 13° and has a total energy of −347 877.514 kcal/mol of which a 436.715 kcal/mol electron correlation energy. The envelope form of the molecule showed an inter-plane angle of 22° and has a total energy of − 347 974.430 kcal/mol involving −436.558 kcal/mol electron correlation energy. The normal coordinates of the molecule were theoretically analyzed and the fundamental vibrational frequencies were calculated. The IR and laser Raman spectra of THT molecule was 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 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 which best match the observed values. The lowest-energy modes of vibration were two molecular out-of-plane deformations, observed at 114 and 166 cm −1. The barrier of ring twisting estimated from the observed ring out-of-plane vibrational mode at 114 cm −1 was estimated.