Characterization and Photofragmentation Studies of the Benzimidazole Homodimer: Evidence for Excited-State Charge-Coupled Proton Transfer.

Abstract

The spectroscopic characterization of the benzimidazole (BIM) homodimer was carried out in a molecular beam in the ground state as well as in the cationic state using the R2PI and RIDIR methods. Primarily, interest in the dimer was due to the observation of a proton-transferred BIM fragment at energies well below its thermodynamic threshold (i.e., barely above the ionization energy of the dimer where fragmentation was not expected). The detailed photofragmentation studies of the homodimer combined with spectroscopic observations and quantum chemical computations of the excited states established that the proton transfer from one subunit to the other occurs via conical intersections connecting the locally excited state, the charge-transfer state, and the ground state. In this study, we have also determined the N-H···N hydrogen bond dissociation energy in the ground state and in the cationic state to be 10.36 ± 0.14 and 27.55 ± 0.20 kcal mol-1, respectively. Incidentally, this happens to be the first such report on the dissociation energy of the N-H···N hydrogen bond.