Theoretical interpretation of the line shape of crystalline adipic acid.

ABSTRACT

A general quantum theoretical approach of the upsilon(X-H) IR line shape of cyclic dimers of weakly H-bonded species in the crystal state is proposed. In this model, the adiabatic approximation (allowing to separate the high-frequency motion from the slow one of the H-bond bridge) is performed for each separate H-bond bridge of the dimer and a strong nonadiabatic correction is introduced into the model via the resonant exchange between the fast-mode excited states of the two moieties. Quantum indirect damping and Fermi resonances are taken into account. The present model reduces satisfactorily to many models in the literature dealing with more special situations. It has been applied to the cyclic dimers of adipic acid in the crystal phase. It correctly fits the experimental line shape of the hydrogenated compound and predicts satisfactorily the evolution in the line shapes with temperature and the change in the line shape with isotopic substitution.