PROTON DYNAMICS AND THE TAUTOMERIZATION POTENTIAL IN BENZOIC-ACID CRYSTALS

Two-proton exchange along the two hydrogen bonds mediates the tautomer ization in benzoic acid (BA) dimers. Optical spectroscopy and quasi-el astic neutron scattering (QENS) have been employed to characterize the proton dynamics in doped and pure BA crystals. The proton motion in B A is governed by a multidimensional potential energy surface (PES), an d recent theoretical methods, based on a perturbative instanton approa ch, to describe tunneling in such PES are presented. This PES is also modulated by the interaction with the solid state environment as manif est by the energy difference between the otherwise equivalent tautomer s. The value of this energy difference in pure crystals is an importan t parameter in the data analysis of NMR and QENS. Both methods give mu tually consistent values that differ significantly from earlier determ inations via infrared and C-13 NMR as well as a recent evaluation usin g neutron diffraction data. The energy difference between tautomers is altered for dimers in the vicinity of impurity molecules. This is the basis for the optical spectroscopic methods, which enable a direct an d accurate determination of the level structure and tautomerization dy namics of these coupled dimers in the limit of very low temperatures, where coherent tunneling is also observed in some cases. Measurements with new impurity molecules make it possible to monitor simultaneously at least 10 different tautomer configurations and prove that the infl uence of the probe molecules on the proton dynamics is small. The tran sition to thermally activated barrier crossing at higher temperatures is accessed via the width of the QENS line that is determined by the i nverse of the proton correlation time. The quantitative data analysis of the scattered intensity as a function of temperature and scattering angle yields the energy difference, A, between the two wells (A/k(B)= 90+/-20 K), the length (0.686 Angstrom, and direction of the proton ju mp vector. These measurements complement NMR investigations presented in the preceding paper.