Transient hole-burning spectroscopy of associated ethanol molecules in the infrared: Structural dynamics and evidence for energy migration

Laenen, R.; Rauscher, C.

doi:10.1063/1.474030

Cited by 48 publications

(46 citation statements)

References 26 publications

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“…[16][17][18] For this system it is also observed that the hydrogen bond is the main accepting mode in the relaxation of the O-H stretch vibration. The energy that is transferred from the O-H stretch vibration to the hydrogen bond causes the hydrogen bond to dissociate, and as a result a transient blueshifted absorption of dissociated ethanol cluster fragments is observed.…”

Section: ͑6͒mentioning

confidence: 91%

Mechanism for vibrational relaxation in water investigated by femtosecond infrared spectroscopy

Nienhuys

Woutersen

Santen

et al. 1999

The Journal of Chemical Physics

213

195

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We present a study on the relaxation of the O–H stretch vibration in a dilute HDO:D2O solution using femtosecond mid-infrared pump-probe spectroscopy. We performed one-color experiments in which the 0→1 vibrational transition is probed at different frequencies, and two-color experiments in which the 1→2 transition is probed. In the one-color experiments, it is observed that the relaxation is faster at the blue side than at the center of the absorption band. Furthermore, it is observed that the vibrational relaxation time T1 shows an anomalous temperature dependence and increases from 0.74±0.01 ps at 298 K to 0.90±0.02 ps at 363 K. These results indicate that the O–H⋯O hydrogen bond forms the dominant accepting mode in the vibrational relaxation of the O–H stretch vibration.

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Section: ͑6͒mentioning

confidence: 91%

Mechanism for vibrational relaxation in water investigated by femtosecond infrared spectroscopy

Nienhuys

Woutersen

Santen

et al. 1999

The Journal of Chemical Physics

213

195

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“…[29][30][31][32][33]66 The main feature of the latter system is that vibrational relaxation of the excited OH (OD) stretching mode results in ultrafast breaking of the hydrogen bond at a time scale shorter than 2 ps. The broken hydrogen bond recovers at a time scale of ∼10 to 20 ps after which the temperature equilibration of the sample settles up.…”

Section: Pathways For Vibrational Energy Relaxationmentioning

confidence: 99%

Hydrogen Bonding and Vibrational Energy Relaxation in Water−Acetonitrile Mixtures

et al. 2004

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We present a study of the effect of hydrogen bonding on vibrational energy relaxation of the OH-stretching mode in pure water and in water-acetonitrile mixtures. The extent of hydrogen bonding is controlled by dissolving water at various concentrations in acetonitrile. Infrared frequency-resolved pump-probe measurements were used to determine the relative abundance of hydrogen-bonded versus non-hydrogen-bonded OH bonds in water-acetonitrile mixtures. Our data show that the main pathway for vibrational relaxation of the OH-stretching mode in pure water involves the overtone of the bending mode. Hydrogen bonding is found to accelerate the population relaxation from 3 ps in dilute solutions to 700 fs in neat water, as a result of increasing overlap between donor and acceptor modes. Hydroxyl groups that initially are not hydrogen bonded have two relaxation pathways: by direct nonresonant relaxation to the bending mode with a time constant of 12 ps or by making a hydrogen bond to a neighboring water molecule first (∼2 ps) and then relaxing as a hydrogen-bonded OH oscillator.

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“…As will be demonstrated below, when the d OD excited state relaxes, hydrogen bonds break [1,9,46], producing photoproduct g ODs. The resulting photoproduct g peak, located above the d band, is visible by T w ¼ 1:2 ps: The diagonal d band progressively contracts to the red as T w increases.…”

Section: Article In Pressmentioning

confidence: 97%

“…Comparison of the center of the preserved d band at T w ¼ 5:0 ps and the center of the initially excited d band (indicated by the horizontal line at 2490 cm À1 ) demonstrates that the preserved d band is contracted to the red and shifted off diagonal along the o m axis. For times longer than B5 ps, the peaks do not change shape significantly, but slowly decay in magnitude on a time scale of 10's of ps because of hydrogen bond recombination [1,9,46]. An important aspect of the 2D correlation spectrum is that the photoproduct g is spectrally separated in the plane from the equilibrium g band (see The T w dependence of the correlation spectra raises a number of questions.…”

Section: Article In Pressmentioning

confidence: 98%

“…Therefore, the decay of the excited state does not completely eliminate the contribution to the signal from the ground state. The ground state signal remains for the hydrogen bond recombination time, which is 10 s of ps [1,9,46]. The detailed analysis of the off diagonal photoproduct g peak will be discussed in a future publication [45].…”

Section: Article In Pressmentioning

confidence: 99%

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

Asbury

Steinel

Fayer

2004

Journal of Luminescence

113

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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 CCl(4) and HOD in H(2)O 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 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 (~100 fs) local fluctuations and essentially identical slow (0.4 and ~2 ps) structural rearrangements. Observation of wavelength dependent dynamics demonstrates that standard theoretical approaches assuming Gaussian fluctuations cannot adequately describe water dynamics.

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Transient hole-burning spectroscopy of associated ethanol molecules in the infrared: Structural dynamics and evidence for energy migration

Abstract: Transient spectral hole burning and hydrogen-bond breaking determined in different solutions of ethanol in deuterated ethanol

Cited by 48 publications

References 26 publications

Mechanism for vibrational relaxation in water investigated by femtosecond infrared spectroscopy

Mechanism for vibrational relaxation in water investigated by femtosecond infrared spectroscopy

Hydrogen Bonding and Vibrational Energy Relaxation in Water−Acetonitrile Mixtures

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

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