Rotational spectrum of trans-trans diethyl ether in the ground and three excited vibrational states

We report the results of a comprehensive reinvestigation of the rotational spectrum of diethyl ether based on broadband millimetre-wave spectra recently recorded at The Ohio State University and in Warsaw, covering the frequency region 108-366 GHz. The data set for the ground vibrational state of trans-trans diethyl ether has been extended to over 2000 lines and improved spectroscopic constants have been determined. Rotational spectra in the first excited vibrational states of the three lowest vibrational modes of trans-trans-diethyl ether, nu(20), nu(39), and nu(12) have been assigned. The nu(20) = 1 and nu(39) = 1 states are near 100 cm(-1) in vibrational term value and are coupled by a strong c-axis Coriolis interaction, which gives rise to many spectacular manifestations in the rotational spectrum. All of these effects have been successfully fitted for a dataset comprising over 3000 transitions, leading to precise determination of the energy difference between these states, (Delta E/hc)=10.400222(5) cm(-1). A newly developed software package for assignment and analysis of broadband spectra is described and made available. (c) 2005 Elsevier Inc. All rights reserved.