Rotational state selection of a CH3I+ ion beam using vacuum ultraviolet-mass-analyzed threshold ionization spectroscopy:: Characterization using photodissociation spectroscopy

The (A) over tilde (2)A(1) <- (X) over tilde E-2(3/2) transition of CH3I+ was investigated by photodissociation (PD) of the cation generated by one-photon mass-analyzed threshold ionization (MATI). Compared to the PD spectrum obtained by excitation of the cation in the main 0-0 band in the MATI spectrum, those obtained by excitation of the cations in the satellite structures showed substantially simplified rotational structures for nondegenerate vibronic bands. Spectral simplification occurred because each satellite consisted mostly of cations with one K quantum number. Spectroscopic constants in the ground vibronic state and in the 2(1)3(5), 2(1)3(8), 3(9), and 3(13) nondegenerate vibrational states in (A) over tilde (2)A(1) were determined via spectral fitting. Also, those in the 2(1)3(n)6(1) (n=1?) degenerate state, which had been reported previously, was improved. The K quantum number in each satellite determined by the present high resolution study was compatible with the prediction by the symmetry selection rule for photoionization. That is, the K quantum number of the ion core in high Rydberg states accessed by one-photon excitation was found to be conserved upon pulsed field ionization. This work demonstrates generation of mass-selected, vibronically selected, and K-selected ion beam by one-photon MATI. (C) 2008 American Institute of Physics.