The rotational spectrum of the ground state of methylamine

Recent progress is reported in measuring, assigning, and fitting the rotational spectrum of the ground vibrational state of methylamine, CH3NH2, a spectrum complicated both by internal rotation of the methyl top and by inversion of the amino group. New measurements of 513 rotational transitions with J up to 30 and K up to 9 were carried out between 49 and 326 GHz using the millimeter-wave spectrometer in Kharkov. After removing the observed quadrupole hyperfine splittings, these new data along with previously published measurements were fitted to a group-theoretical high-barrier tunneling Hamiltonian from the literature, using 53 parameters to give an overall weighted standard deviation of 0.80 for 850 far-infrared and 673 microwave transitions in the ground state. The root-mean-square deviation of 0.018 MHz obtained for 346 millimeter-wave transitions measured with 0.020 MHz uncertainty represents an approximately 30-fold improvement in fitting accuracy over past attempts. (C) 2004 Elsevier Inc. All rights reserved.