The puzzling hyper-fine structure and an accurate equilibrium geometry of succinic anhydride

Abstract

An accurate semiexperimental equilibrium structure of succinic anhydride has been determined from a combination of experiment and theory. The cm-wave and mm-wave rotational spectra of succinic anhydride, 3,4-dihydrofuran-2,5-dione, were recorded in a pulsed supersonic jet using Fourier-transform microwave spectroscopy and in a free-jet using mm-wave absorption spectroscopy. Many lines in the cm-wave spectrum show fine structure and after eliminating all other possibilities the origin of this fine structure is determined to be from spin–spin interaction. Accurate rotational and quartic centrifugal distortion constants are determined. Assignments of ¹³C and ¹⁸O singly substituted isotopologues in natural abundance were used to obtain a substitution geometry for the heavy atoms of succinic anhydride. Theoretical approaches permitted the calculation of a Born–Oppenheimer ab initio structure and the determination of a semiexperimental equilibrium structure in which computed rovibrational corrections were utilized to convert vibrational ground state rotational constants into equilibrium constants. The agreement between the semiexperimental structure and the Born–Oppenheimer ab initio structure is excellent. Succinic anhydride has been shown to have a planar heavy atom equilibrium structure with the effects of a large amplitude vibration apparent in the resultant rotational constants.