Two-Color Resonant Two-Photon Mass-Analyzed Threshold Ionization of 2,4-Difluoroanisole and the Additivity Relation of Ionization Energy.

We used the two-color resonant two-photon ionization and mass-analyzed threshold ionization spectroscopic techniques to record the vibronic, photoionization efficiency, and cation spectra of 2,4-difluoroanisole. The cation spectra were obtained through ionization via seven intermediate vibronic states, which involved out-of-plane ring-F, in-plane ring-F, and ring-OCH bending vibrations as well as in-plane ring deformation vibrations. The band origin of the S ← S electronic transition of 2,4-difluoroanisole appeared at 35 556 ± 2 cm, and the adiabatic ionization energy was determined to be 67 568 ± 5 cm. The experimental data provided information on the active vibrations of aforementioned compound in the electronically excited state S and ground cationic state D. A comparison of the experimental data obtained for 2,4-difluoroanisole in this study with the data obtained for other fluorine-substituted benzenes in previous studies indicated that the nature, location, and number of substituents influence electronic transition energy, ionization energy, and molecular vibration. In addition, a simple additivity relation might exist for predicting the ionization energy of multiply substituted benzene derivatives.