Vibrational structures of methylamine isotopomers in the predissociative (A)over-tilde states:: CH3NHD, CD3NH2, CD3NHD, and CD3ND2

Mass-resolved two-photon (1+1) resonance-enhanced multiphoton ionization spectra of the A-X transitions of various methylamine isotopomers (CH3NHD, CD3NH2, CD3NHD, and CD3ND2) cooled in the supersonic jet expansion have been measured and analyzed. The band analysis using the Hamiltonian for the internal and overall rotational motions provides the accurate vibrational band positions, allowing for unambiguous assignments for all observed vibrational bands of methylamine isotopomers in the A states. Amino wagging (nu(9)) and methyl rocking (nu(7)) modes are found to be Franck-Condon active, and associated anharmonicity constants are precisely determined to give the detailed shape of the potential energy surface in the vicinity of the minimum electronic molecular structure. The barrier height for the nearly free internal rotation about the C-N bond in the A state is calculated to be strongly dependent on the excitation of the other higher-frequency vibrational modes, and it is found that the trend is consistent with the experiment. Experimentally measured spectroscopic constants are compared with ab initio calculations, confirming all vibronic assignments. Experimental and theoretical results on all possible H/D isotopomers of methylamine in this work, with the earlier report on CH3NH2 and CH3ND2 Baek , [J. Chem. Phys. 118, 11026 (2003)], provide the complete spectroscopic characterization of the A state of methylamine. (c) 2006 American Institute of Physics.