Cooperative proton transfer and tunneling in dye doped benzoic acid crystals

Abstract

In seleno-indigo doped benzoic acid crystals, the energy level structure of a pair of benzoic acid dimers coupled to the impurity center is characterized by optical spectroscopy and transient hole burning in electric fields. The lowest energy states involve degenerate, polar proton configurations. Proton tunneling lifts this degeneracy. The tunneling matrix element for proton transfer in a benzoic acid dimer equals 6.5±1.5 GHz, a value comparable to those found with other guest molecules. Relaxation between the two ground state levels involves the concerted motion of four protons and determines the intensity distribution of the fine structure observed in hole burning.