Utilizing the vacuum ultraviolet (VUV) synchrotron radiation and a double imaging photoelectron photoion coincidence (i(2)PEPICO) technique, we have measured the adiabatic ionization energies (AIEs) of the overlapped A(2)A1 and B(2)E electronic states of CH3Cl(+) and CH3F(+) ions. We show that the two overlapped electronic states can be separated in the electron and ion kinetic energy correlation diagrams based on their state-specific dissociation dynamics, leading to different kinetic energies released in dissociation, along the CH3(+) fragmentation channel. Thus the correlation diagrams yielded values of 13.67 ± 0.03 and 14.77 ± 0.03 eV for the AIEs of the A(2)A1 and B(2)E states of CH3Cl(+), and 16.08 ± 0.03 and 17.00 ± 0.05 eV for CH3F(+), respectively. This method can be generalized to separate ionic states that are otherwise overlapped in normal photoelectron spectra (PES), especially by combining VUV sources and electron/ion coincidence techniques.
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