Fourier Transform Microwave Spectrum of the Nitrogen Molecule–Ethylene Oxide Complex: Intracomplex Motions

Abstract

The rotational spectra of the N2-ethylene oxide (EO) complex were measured in the frequency region from 4 to 27 GHz by Fourier transform microwave spectroscopy, paying particular attention to intracomplex motions. The isotopologues with enriched (15)N2 or (15)NN as a moiety were also investigated. We have observed spectra of a strong/weak pair for each of the ortho and para states of the (14)N2-EO and (15)N2-EO species, which indicated that the complex existed in four distinct states. We interpreted, on the basis of the observed relative intensities, that these states were generated primarily by the exchange of the nitrogen atoms of the N2 moiety, followed by that of the two CH2 groups in the EO molecule. The (15)NN-EO species was found to consist of two isomers, one with the (15)N in the inner expressed as N(15)N-EO and the other in the outer position designated as (15)NN-EO, and the spectra of both isomers were accompanied by one weak set of satellites. The observed spectra were rotationally assigned by using sum rules and were analyzed by the asymmetric-rotor program of S-reduction, with the standard deviation of less than 10 kHz. We have found some of the molecular parameters like A, D(JK), and D(K) to be correlated between the two pairs of the spectra, and also, to much less extent, between the strong and weak members. The differences in these molecular parameters between the four sets were explained by the first-order Coriolis interaction between the "ground" and "excited" states generated by a combination of the two internal motions corresponding to the exchanges of the equivalent atoms and/or groups in the N2 and EO constituents of the complex. These internal motions were simulated by the 2-fold internal rotations of the two moieties. We have carried out ab initio molecular orbital calculations at the level of MP2 with basis sets 6-311++G(d,p), aug-cc-pVDZ, and aug-cc-pVTZ, to complement the information on the intracomplex motions obtained from the observed rotational spectra.