CH3(+) Formation in the Dissociation of Energy-Selected CH3F(+) Studied by Double Imaging Electron/Ion Coincidences.

The dissociation of energy-selected methyl fluoride ion CH3F(+) along the CH3(+) and F formation channel has been investigated in detail in the 12.2-19.8 eV energy range. Three low-lying electronic states of the CH3F(+) ion, X(2)E, A(2)A1, and B(2)E, were prepared and analyzed by the method of double imaging photoelectron photoion coincidence (i(2)PEPICO). Three types of CH3(+) fragment ions corresponding to the dissociation of X(2)E, A(2)A1, and B(2)E electronic states have been observed and identified through their kinetic energy release distribution (KERD) curves, showing that the dissociation of the CH3F(+) ion in the different electronic states along the CH3(+) formation channel is state-specific, even outside of the Franck-Condon region. Highly excited vibrational levels of the X(2)E ground state can be populated through a resonant or near-resonant autoionization process and undergo vibrational predissociation into CH3(+) fragment ions. The A(2)A1 first excited state is repulsive along the F-loss coordinate, and its dissociation is direct and fast. The CH3F(+) ions in the B(2)E excited state first undergo an internal conversion toward the hot cation ground state X(2)E and then statistically dissociate into CH3(+) and F fragments.