Mass-analyzed threshold ionization (MATI) and two-color resonant two-photon ionization methods were
used for the determination of the ionization energy (IE) of o-fluoroaniline (OFA) and the vibrational levels of
the OFA cation. The MATI spectra were recorded ia the 00 vibrationless and the 10b1, 16a1, 11 and 121 vibrational
levels of the S1 state. The adiabatic IE of OFA was found to be 63644±5 cm−1 (7.8904±0.0006 eV)
by MATI spectroscopy. The observed vibrations of the OFA cation include the in-plane ring CCC bending,
CH bending, CF bending, CN bending and CN stretching, as well as some out-of-plane ring vibrations.
The experimental findings are well supported by ab initio and density functional theory calculations.
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