Lamb-dip spectroscopy of the C-N stretching band of methylamine by using frequency-tunable microwave sidebands of CO2 laser lines.

Lamb-dip spectroscopy of the C-N stretching band of methylamine has been systematically extended to P-, Q-, and R-branch by using microwave sidebands of a large number of CO2 laser lines as frequency-tunable infrared sources in a sub-Doppler spectrometer. Lamb-dip signals of more than 150 spectral lines have been observed with a resolution of 0.4 MHz and their frequencies have been precisely measured with an accuracy of ±0.1 MHz. More than 30 closed combination loops have been formed, which unambiguously confirm the assignments. For over 150 vibrational excited levels in 27 substates, refined term values have been determined and expanded in J(J + 1) power-series to determine the substate origins and the effective rotational constants. For transitions with Aa torsion-inversion symmetry in torsional state υt = 0, 57 K-doublet lines displaying asymmetry splittings have been observed and the splitting constants for levels with K = 1, 2, and 3 in the excited states have been determined. Our results provide accurate experimental information for spectroscopic studies of the interesting vibrational perturbations and intermode interactions related to the C-N stretching mode, directly support astronomical surveys, and are very relevant in practice to identification and frequency determination of the CO2-laser-pumped far-infrared laser lines of methylamine.

High-resolution spectroscopy of the C-N stretching band of methylamine.

The C-N stretching infrared fundamental of CH(3)NH(2) has been investigated by high-resolution laser sideband and Fourier transform synchrotron spectroscopy to explore the energy level structure and to look for possible interactions with high-lying torsional levels of the ground state and other vibrational modes. The spectrum is complicated by two coupled large-amplitude motions in the molecule, the CH(3) torsion and the NH(2) inversion, which lead to rich spectral structure with a wide range of energy level splittings and relative line intensities. Numerous sub-bands have been assigned for K values ranging up to 12 for the stronger a inversion species for the v(t) = 0 torsional state, along with many of the weaker sub-bands of the s species. The C-N stretching sub-state origins have been determined by fitting the upper-state term values to J(J + 1) power-series expansions. For comparison with the ground-state behaviour, both ground and C-N stretch origins have been fitted to a phenomenological Fourier series model that produces an interesting pattern with the differing periodicities of the torsional and inversion energies. The amplitude of the torsional energy oscillation increases substantially for the C-N stretch, while the amplitude of the inversion energy oscillation is relatively unchanged. Independent inertial scale factors ρ were fitted for the torsion and the inversion and differ significantly in the upper state. The C-N stretching vibrational energy is determined to be 1044.817 cm(-1), while the effective upper state B-value is 0.7318 cm(-1). Several anharmonic resonances with v(t) = 4 ground-state levels have been observed and partially characterized. A variety of J-localized level-crossing resonances have also been seen, five of which display forbidden transitions arising from intensity borrowing that allow determination of the interaction coupling constants.

Precision Lamb-dip infrared spectra of the C-N stretching band of CH(3)NH(2) with a CO(2)-laser/microwave-sideband spectrometer.

We report saturation dip spectroscopy in the C-N stretching band of CH(3)NH(2) with a resolution of 0.4 MHz and an accuracy of 0.1 MHz by use of a CO(2)-laser/microwave-sideband spectrometer. The wide tunability, Lamb-dip resolution, absolute frequency accuracy, and high sensitivity of our dual-mode instrument were all key features in making precise measurements for a range of lines in the densely crowded spectrum with its complex pattern of splittings arising from the large-amplitude CH(3) torsion and NH(2) inversion. We focused on achieving resolution and assignment of transitions within the highly blended Q branch of the C-N stretch and on observations of the important K=0 sequences of Aa and Ea torsion-inversion symmetry. Term values of the latter were fitted to J(J+1) power-series expansions to obtain the K=0 C-N stretching effective B values and substate origins, from which calculated ground-state substate energies were subtracted to yield values of 1044.7061 and 1044.8011 cm(-1) for the Aa and Ea subband origins, respectively. We thereby estimate a mean value of 1044.75(5) cm(-1) for the vibrational band origin and 0.7323(5) cm(-1) for the effective upper-state B value for the C-N stretching fundamental of CH(3)NH(2).