Localized excitations in hydrogen-bonded molecular crystals

Localized excitations analogous to the small Holstein polaron, to localized modes in alkali halides, and to localized excitonic states, are postulated for a set of internal vibrational modes in crystalline acetanilide. The theoretical framework in which one can describe the characteristics of the ir and Raman spectroscopy peaks associated with these localized states is adequately provided by the Davydov model (formally equivalent to the Holstein polaron model). The possible low-lying excitations arising from this model are determined using a variational approach. Hence, the contribution to the spectral function due to each type of excitation can be calculated. The internal modes of chief concern here are the amide-I (C?O stretch) and the N---H stretch modes for which we demonstrate consistency of the theoretical model with the available ir data. Past theoretical approaches will be discussed and reasons why one should prefer one description over another will be examined.