Vibrational echo correlation spectroscopy probes of hydrogen bond dynamics in water and methanol

John B. Asbury, Tobias Steinel, M. D. Fayer

Research output: Contribution to journalConference article

72 Citations (Scopus)

Abstract

Multidimensional vibrational echo correlation spectroscopy with full phase resolution 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 (<50fs, <4 cycles of light) produced to date. The pulses have sufficient spectral bandwidth to span the very broad (>00cm-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 experimental results along with detailed calculations indicate the strongest hydrogen bonds are selectively broken through a non-equilibrium 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 aqueous systems. The analysis of the 2D band shapes demonstrates that different hydrogen bonded species are subject to distinct (wavelength dependent) ultrafast (∼100fs) local fluctuations and essentially identical slow (0.4 and ∼2ps) structural rearrangements. Observation of wavelength dependent dynamics demonstrates that standard theoretical approaches assuming Gaussian fluctuations cannot adequately describe water dynamics.

Original languageEnglish (US)
Pages (from-to)271-286
Number of pages16
JournalJournal of Luminescence
Volume107
Issue number1-4
DOIs
StatePublished - May 1 2004
EventProceedings of the 8th International Meeting on Hole Burning, HBSM 2003 - Bozeman, MT., United States
Duration: Jul 26 2003Jul 31 2003

Fingerprint

Methanol
Hydrogen
Spectrum Analysis
echoes
Hydrogen bonds
methyl alcohol
Spectroscopy
hydrogen bonds
Water
probes
oligomers
Oligomers
Hydroxyl Radical
water
spectroscopy
Wavelength
Population dynamics
hydrogen
molecular relaxation
wavelengths

All Science Journal Classification (ASJC) codes

  • Biophysics
  • Atomic and Molecular Physics, and Optics
  • Chemistry(all)
  • Biochemistry
  • Condensed Matter Physics

Cite this

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abstract = "Multidimensional vibrational echo correlation spectroscopy with full phase resolution 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 (<50fs, <4 cycles of light) produced to date. The pulses have sufficient spectral bandwidth to span the very broad (>00cm-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 experimental results along with detailed calculations indicate the strongest hydrogen bonds are selectively broken through a non-equilibrium 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 aqueous systems. The analysis of the 2D band shapes demonstrates that different hydrogen bonded species are subject to distinct (wavelength dependent) ultrafast (∼100fs) local fluctuations and essentially identical slow (0.4 and ∼2ps) structural rearrangements. Observation of wavelength dependent dynamics demonstrates that standard theoretical approaches assuming Gaussian fluctuations cannot adequately describe water dynamics.",
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Vibrational echo correlation spectroscopy probes of hydrogen bond dynamics in water and methanol. / Asbury, John B.; Steinel, Tobias; Fayer, M. D.

In: Journal of Luminescence, Vol. 107, No. 1-4, 01.05.2004, p. 271-286.

Research output: Contribution to journalConference article

TY - JOUR

T1 - Vibrational echo correlation spectroscopy probes of hydrogen bond dynamics in water and methanol

AU - Asbury, John B.

AU - Steinel, Tobias

AU - Fayer, M. D.

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N2 - Multidimensional vibrational echo correlation spectroscopy with full phase resolution 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 (<50fs, <4 cycles of light) produced to date. The pulses have sufficient spectral bandwidth to span the very broad (>00cm-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 experimental results along with detailed calculations indicate the strongest hydrogen bonds are selectively broken through a non-equilibrium 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 aqueous systems. The analysis of the 2D band shapes demonstrates that different hydrogen bonded species are subject to distinct (wavelength dependent) ultrafast (∼100fs) local fluctuations and essentially identical slow (0.4 and ∼2ps) structural rearrangements. Observation of wavelength dependent dynamics demonstrates that standard theoretical approaches assuming Gaussian fluctuations cannot adequately describe water dynamics.

AB - Multidimensional vibrational echo correlation spectroscopy with full phase resolution 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 (<50fs, <4 cycles of light) produced to date. The pulses have sufficient spectral bandwidth to span the very broad (>00cm-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 experimental results along with detailed calculations indicate the strongest hydrogen bonds are selectively broken through a non-equilibrium 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 aqueous systems. The analysis of the 2D band shapes demonstrates that different hydrogen bonded species are subject to distinct (wavelength dependent) ultrafast (∼100fs) local fluctuations and essentially identical slow (0.4 and ∼2ps) structural rearrangements. Observation of wavelength dependent dynamics demonstrates that standard theoretical approaches assuming Gaussian fluctuations cannot adequately describe water dynamics.

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