Multidimensional infrared spectroscopy of the N-H bond motions in formamide.
The heterodyned two-dimensional (2D) IR spectra and equilibrium dynamics of the N-H stretching motion of DCONHD in deuterated formamide, DCOND(2), were studied with 80 fs pulses at 3 microm. The time evolution of the heterodyned 2D IR spectra, pump-probe spectra, and photon echo peak shift demonstrate that interstate dynamics is occurring by relaxation of the original N-H excitation. The N-H vibrational frequency correlation function can be expressed as a sum of three exponentials with correlation times 0.24 ps, 0.8 ps, and 11 ps. The intermediate component is attributed to motions of the N-Hcdots, three dots, centeredO unit involving only slight angular variations of the N-H bond. The slow component is attributed to the structure breaking and making. The anisotropy decay confirmed that the significant angular N-H bond motion occurs on the 11 ps time scale. The fast component, which is the least well determined, might correspond to the modulation of the H-bond distance without angular motion. The correlation coefficient between the pumped and relaxed state distributions was +0.51, implying that the excited state phase memory is only slightly diminished by the relaxation of the N-H excitation. The relaxed modes are concluded to be local to the driven N-H mode.
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
Jaehun
J
Park
Jeong-Hyon
JH
Ha
Robin M
RM
Hochstrasser
D003198:Computer Simulation; D005559:Formamides / Q000737:chemistry*; D006860:Hydrogen Bonding; D008956:Models, Chemical; D013055:Spectrophotometry, Infrared
D005559:Formamides; C031066:formamide