Watching Vibrational Energy Transfer in Liquids with Atomic Spatial Resolution

Ultrafast spectroscopy was used to study vibrational energy transfer between vibrational reporter groups on different parts of a molecule in a liquid. When OH stretching vibrations of different alcohols were excited by mid-infrared laser pulses, vibrational energy was observed to move through intervening CH2 or CH groups, taking steps up and down in energy, ending up at terminal CH3 groups. For each additional CH2 group in the path between OH and CH3, the time for vibrational energy transfer increased by about 0.4 picosecond.

[1]  D. Dlott,et al.  Three-dimensional spectroscopy of vibrational energy relaxation in liquid methanol , 2000 .

[2]  C. Rauscher,et al.  Time-resolved infrared spectroscopy of ethanol monomers in liquid solution: molecular reorientation and energy relaxation times , 1997 .

[3]  S. Mukamel,et al.  Energy gap law for vibrational relaxation of a molecule in a dense medium , 1975 .

[4]  D. Dlott,et al.  Ultrafast vibrational energy redistribution within C H and O H stretching modes of liquid methanol , 2000 .

[5]  D. Dlott,et al.  Vibrational energy redistribution in liquid benzene , 1999 .

[6]  D. Dlott,et al.  Ultrafast infrared–Raman studies of vibrational energy redistribution in polyatomic liquids , 2000 .

[7]  W. Kaiser,et al.  Vibrational dynamics of liquids and solids investigated by picosecond light pulses , 1978 .

[8]  D. Dlott,et al.  Ultrafast Mode-Specific Intermolecular Vibrational Energy Transfer to Liquid Nitromethane , 1995 .

[9]  W. Reinhardt,et al.  Nonlinear resonances and vibrational energy flow in model hydrocarbon chains , 1983 .

[10]  E. Heilweil,et al.  Population lifetimes of OH(v=1) and OD(v=1) stretching vibrations of alcohols and silanols in dilute solution , 1986 .

[11]  S. Woutersen,et al.  A Femtosecond Mid-infrared Pumpprobe Study Of Hydrogen-bonding In Ethanol , 1997, QELS '97., Summaries of Papers Presented at the Quantum Electronics and Laser Science Conference.

[12]  V. M. Kenkre,et al.  Theory of vibrational relaxation of polyatomic molecules in liquids , 1994 .

[13]  Robin M. Hochstrasser,et al.  Transition State Dynamics and Relaxation Processes in Solutions: A Frontier of Physical Chemistry , 1996 .

[14]  K. Simeonidis,et al.  Energy relaxation and reorientation of the OH mode of simple alcohol molecules in different solvents monitored by transient IR spectroscopy , 1999 .

[15]  D. Dlott,et al.  Vibrational Energy Redistribution in Polyatomic Liquids: Ultrafast IR−Raman Spectroscopy of Acetonitrile , 1998 .

[16]  D. Dlott,et al.  High-power picosecond mid-infrared optical parametric amplifier for infrared Raman spectroscopy. , 1997, Optics letters.

[17]  A. Laubereau,et al.  Transient Hole Burning in the Infrared in an Ethanol Solution , 1997 .

[18]  Huib J. Bakker,et al.  Resonant intermolecular transfer of vibrational energy in liquid water , 1999, Nature.