Observation of rotamers of <i>m</i>-aminobenzoic acid: Zero kinetic energy photoelectron and hole-burning resonantly enhanced multiphoton ionization spectroscopy

Abstract

We report studies of supersonically cooled m-aminobenzoic acid using two-color resonantly enhanced multiphoton ionization (REMPI) and two-color zero kinetic energy (ZEKE) photoelectron spectroscopy. Two conformers have been identified and characterized using the hole-burning method in the REMPI experiment. With the aid of ab initio and density functional calculations, vibrational modes of the first electronically excited state (S1) of the neutral species and those of the ground state cation (D0) have been assigned, and the adiabatic ionization potentials have been determined for both conformers. The REMPI spectra are dominated by in-plane motions of the substituents and ring deformation modes. A propensity of Δv=0, where Δv is the change in vibrational quantum number from the S1 to the D0 state, is observed in the ZEKE spectra. The origin of this behavior is discussed in the context of electron back donation from the two substituents in the excited state and in the cationic state. Comparisons of these results with those of p-aminobenzoic acid will be analyzed.