Spectral response of crystalline acetanilide and N-methylacetamide:: Vibrational self-trapping in hydrogen-bonded crystals -: art. no. 214301

Femtosecond pump-probe and Fourier transform infrared spectroscopy is applied to compare the spectral response of the amide I band and the NH-stretching band of acetanilide (ACN) and N-methylacetamide (NMA), as well as their deuterated derivatives. Both molecules form hydrogen-bonded molecular crystals that are regarded to be model systems for polypeptides and proteins. The amide I bands of both ACN and NMA show a temperature-dependent sideband, while the NH bands are accompanied by a sequence of equidistantly spaced satellite peaks. These spectral anomalies are interpreted as a signature of vibrational self-trapping. Two different types of states can be identified in both crystals in the pump-probe signal: a delocalized free-exciton state and a set of localized self-trapped states. The phonons that mediate self-trapping in ACN and deuterated ACN are identified by their temperature dependence, confirming our previous results. The study shows that the substructure of the NH band in NMA (amide A and amide B bands) originates, at least partly, from vibrational self-trapping and not, as often assumed, from a Fermi resonance.