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- Autor(en):
- Asbury, John B.; Steinel, Tobias; Stromberg, C.; Gaffney, K. J.; Piletic, I. R.; Fayer, M. D.
- Titel:
- Hydrogen bond breaking probed with multidimensional stimulated vibrational echo correlation spectroscopy
- Abstract:
- H bond population dynamics are extricated with exceptional detail using ultrafast (<50 fs) IR multidimensional stimulated vibrational echo correlation spectroscopy with full phase information and frequency resolved IR pump-probe expts. performed on the hydroxyl stretch of MeOH-OD oligomers in CCl4. H bond breaking makes it possible to acquire data for times much greater than the hydroxyl stretch vibrational lifetime. The correlation spectra and detailed calcns. demonstrate that vibrational relaxation leads to H bond breaking for oligomers that have hydroxyl stretch frequencies on the low energy (red) side of the hydroxyl stretch spectrum, the spectral region that is assocd. with the strongest H bonds. Frequency resolved pump-probe data support the conclusions drawn from the correlation spectra. Using a global fit to the pump-probe spectra, in conjunction with assignments made possible through the correlation spectra, the residual ground state and photoproduct of H bond breaking were prepd. near their thermal equil. distribution. The spectrum of the H bond breaking photoproduct and the residual ground state approach the steady-state temp. difference spectrum on the tens of picoseconds time scale, indicating the system thermalizes on this time scale. [on SciFinder(R)]
- Stichworte:
- Hydrogen bond Photolysis Reaction mechanism Stretching vibration Vibrational relaxation Vibrational transition (hydrogen bond breaking probed with multidimensional stimulated vibrational echo correlation spectroscopy) Oligomers Role: PEP (Physical, engineering or chemical process), PRP (Properties), PYP (Physical process), RCT (Reactant), PROC (Process), RACT (Reactant or reagent) (hydrogen bond breaking probed with multidimensional stimulated vibrational echo correl Photon echo (vibrational hyd... »
- Kongresstitel:
- CAN 140:206758 73-3 Optical, Electron, and Mass Spectroscopy and Other Related Properties Department of Chemistry, Stanford University, Stanford, CA, USA. Journal 0021-9606 4206-31-9 (Methanol-d1) Role: PEP (Physical, engineering or chemical process), PRP (Properties), PYP (Physical process), RCT (Reactant), PROC (Process), RACT (Reactant or reagent) (hydrogen bond breaking probed with multidimensional stimulated vibrational echo correlation spectroscopy); 56-23-5 (Carbon tetrachloride) Role: N... »
- Zeitschriftentitel:
- J. Chem. Phys.
- Jahr:
- 2003
- Band / Volume:
- 119
- Heft / Issue:
- 24
- Seitenangaben Beitrag:
- 12981-12997
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