Abstract
Abstract We applied the two-color resonant two-photon ionization and mass-analyzed threshold ionization techniques to record the vibrationally resolved spectra of the selected isotopomers of o -chloroanisole in the electronically excited S 1 and cationic ground D 0 states. As supported by our theoretical calculations, only the trans form of o -chloroanisole involves in the two-photon photoexcitation and ionization processes. The band origins of the S 1 ← S 0 electronic transition and adiabatic ionization energies for the 35 Cl and 37 Cl isotopomers of o -chloroanisole are found to be the same within our detection limit, with the values of 35 745 ± 2 and 66 982 ± 5 cm −1 , respectively. The general spectral features of the two isotopomers are nearly identical and result from in-plane ring deformation and substituent-sensitive bending and stretching as well as the CH 3 torsional motions.
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