The millimeter- and submillimeter-wave spectrum of the trans–gauche conformer of diethyl ether

Abstract

The results of a first investigation of the rotational spectrum of the trans–gauche conformer of diethyl ether are reported. Two spectrometers have been used to measure the spectrum in the millimeter-wave and submillimeter-wave regions and a total of 1090 absorption line frequencies in the range 108–366 GHz were obtained and analyzed. Of these lines, 902 were measured with a spectrometer employing the fast scan submillimeter spectroscopic technique (FASSST) at Ohio State and the remaining 188 were measured with the phase-lock two-loop system (PLL) in Warsaw. The spectrum was fit to within experimental accuracy with the use of the A-reduced Watson Hamiltonian. Based on relative intensity measurements, the percentage of diethyl ether at room temperature in the trans–gauche conformer was found to be 30.5(13)%, in good agreement with prior spectroscopic values and an ab initio determination based on an energy difference of 5.40 kJ mol −1 (452 cm −1) between the excited trans–gauche and ground trans–trans conformers. This work also stimulated a critical evaluation of the data acquisition and calibration procedure of the FAAAST spectrometer, the results of which will be discussed.