Fourier Transform Microwave Spectra of the Nitrogen Molecule–Ethylene Sulfide and Nitrogen Molecule–Dimethyl Sulfide Complexes

Abstract

We recorded the rotational spectra of N2–ethylene sulfide (ES) and N2–dimethyl sulfide (DMS) including the 15N2 and 15N14N isotopomers in the frequency range of 5–25 GHz by using a Fourier transform microwave spectrometer. The b-type transitions for the ortho and para states of 14N2–ES and 15N2–ES and c-type transitions of 14N2–DMS and 15N2–DMS were observed. The 15N14N–ES and 15N14N–DMS species were found to exist in two isomeric forms: inner (14N15N–ES and 14N15N–DMS) and outer (15N14N–ES and 15N14N–DMS). Neither the −ES nor −DMS complexes showed weak accompanying spectra, which had been observed for N2–ethylene oxide (EO). This is because the potential barriers to internal rotation of ES and DMS are higher than that of EO. The spectra were analyzed by an A-reduced asymmetric-top rotational program with less than 4 kHz standard deviation, except for the 15N14N–DMS and 14N15N–DMS complexes. Rotational, centrifugal distortion, and nuclear electric quadrupole coupling constants were determined by the spectral analysis. The V 3 potential barrier to internal rotation of the two equivalent methyl groups of DMS in the ortho and para states of the 15N2–DMS complex was determined to be about 740 cm–1. We performed ab initio calculations in order to complement the information on the intracomplex motions obtained from the experimental spectra.