We studied the pathways of vibrational energy relaxation of the amide I (similar to 1660 cm(-1)) and amide II (similar to 1560 cm(-1)) vibrational modes of N-methylacetamide (NMA) in CCl4 solution using two-color femtosecond vibrational spectroscopy. We measured the transient spectral dynamics upon excitation of each of these amide modes. The results show that there is no energy transfer between the amide I (AI) and amide II (AII) modes. Instead we find that the vibrational energy is transferred on a picosecond time scale to a common combination tone of lower-frequency modes. By use of polarization-resolved femtosecond pump probe measurements we also study the reorientation dynamics of the NMA molecules and the relative angle between the transition dipole moments of the AI and AII vibrations. The spectral dynamics at later times after the excitation (>40 ps) reveal the presence of a dissociation process of the NMA aggregates, trimers, and higher order structures into dimers and monomers. By measuring the dissociation kinetics at different temperatures, we determined the activation energy of this dissociation E-a = 35 +/- 3 kJ mol(-1).

T.S. Shimizu (Thomas)
J. Phys. Chem. A
Ultrafast Spectroscopy

Piatkowski, L., & Bakker, H. (2010). Vibrational relaxation pathways of Al and All modes in N-methylacetamide clusters. J. Phys. Chem. A, 114(43), 11462–11470. doi:10.1021/jp107590b