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- Document type:
- Zeitschriftenaufsatz
- Author(s):
- Asbury, John B.; Steinel, Tobias; Fayer, M. D.
- Title:
- Vibrational echo correlation spectroscopy probes of hydrogen bond dynamics in water and methanol
- Abstract:
- Multidimensional vibrational echo correlation spectroscopy with full phase resoln. is used to measure hydrogen bond dynamics in water and methanol. The OD hydroxyl stretches of methanol-OD oligomers in CCl4 and HOD in H2O are studied using the shortest mid-IR pulses (<50 fs, <4 cycles of light) produced to date. The pulses have sufficient spectral bandwidth to span the very broad (>400 cm-1) spectrum of the 0-1 and 1-2 transitions. Hydrogen bond population dynamics are extricated with exceptional detail in MeOD oligomers because the different hydrogen bonded species are spectrally distinct. The exptl. results along with detailed calcns. indicate the strongest hydrogen bonds are selectively broken through a non-equil. relaxation pathway following vibrational relaxation of the hydroxyl stretch. The correlation spectra are also a sensitive probe of the fluctuations in water and provide a stringent test of water models that are widely used in simulations of aq. systems. The anal. of the 2D band shapes demonstrates that different hydrogen bonded species are subject to distinct (wavelength dependent) ultrafast (∼100 fs) local fluctuations and essentially identical slow (0.4 and ∼2 ps) structural rearrangements. Observation of wavelength dependent dynamics demonstrates that std. theor. approaches assuming Gaussian fluctuations cannot adequately describe water dynamics. [on SciFinder(R)]
- Keywords:
- Stretching vibration (hydroxyl vibrational echo correlation spectroscopy probes of hydrogen bond dynamics in water and methanol) Laser radiation (pulsed IR vibrational echo correlation spectroscopy probes of hydrogen bond dynamics in water and methanol) Fluctuations Hydrogen bond Liquid structure Vibrational relaxation Vibrational spectroscopy Vibrational transition (vibrational echo correlation spectroscopy probes of hydrogen bond dynamics in water and methanol) Photon echo (vibrational vibrati... »
- Congress title:
- CAN 141:181136 73-3 Optical, Electron, and Mass Spectroscopy and Other Related Properties Department of Chemistry, Stanford University, Stanford, CA, USA. Journal 0022-2313 4206-31-9 (Methanol-d1); 14940-63-7 (Water-d) Role: PRP (Properties) (vibrational echo correlation spectroscopy probes of hydrogen bond dynamics in water and methanol)
- Journal title:
- J. Lumin.
- Year:
- 2004
- Journal volume:
- 107
- Journal issue:
- 1-4
- Pages contribution:
- 271-286
- Fulltext / DOI:
- doi:10.1016/j.jlumin.2003.12.035
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