Ultrafast Raman-induced Kerr-effect of water: Single molecule versus collective motions

Winkler, Kathrin; Lindner, Jörg; Bürsing, Helge; Vöhringer, Peter

doi:10.1063/1.1288690

Cited by 138 publications

(136 citation statements)

References 52 publications

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“…The longest time scales in aqueous relaxation were previously attributed to relaxation of the hydrogen bond network of bulk water. 70 Recently, Vöhringer and co-workers 1,7 argued from comparison of their OKE data with NMR studies that the slow picosecond component stems from single molecule motion. On the other hand, it seems difficult to make a clear distinction between a diffusive single molecule process and collective motion in a liquid, since single molecule diffusion can be considered as the result of a molecule moving stochastically in the potential created by the other molecules and involving formation and breaking of hydrogen bonds, making it a process that inherently involves more than the single molecule under consideration.…”

Section: Discussionmentioning

confidence: 99%

“…It is worth noting, that a decay time slower than 1 ps was not observed in previous time-dependent Stokes shift measurements 11,24,29 but was seen in photon echo peak shift 7,8 and OKE measurements. 1 As outlined above, within the Debye model, our experiments should be sensitive to the longitudinal decay time τ L of the dielectric relaxation, which is faster than the Debye relaxation time. On the other hand, it is well-known that water shows a much more complex behavior and cannot adequately be described with a single Debye relaxation.…”

Section: Discussionmentioning

confidence: 99%

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Aqueous Solvation Dynamics at Metal Oxide Surfaces

et al. 2006

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Broadband transient absorption (TA) spectroscopy, three-pulse photon echo peak shift (3PEPS), and anisotropy decay measurements were used to study the solvation dynamics in bulk water and interfacial water at ZrO 2 surfaces, using Eosin Y as a probe. The 3PEPS results show a multiexponential behavior with two subpicosecond components that are similar in bulk and interfacial water, while a third component of several picoseconds is significantly lengthened at the interface. The bandwidth correlation function from TA spectra exhibits the same behavior, and the TA spectra are well reproduced using the doorway-window picture with the time constants from PEPS. Our results suggest that interfacial water is restricted to a thickness of less than 5 Å. Also the high-frequency collective dynamics of water does not seem to be affected by the interface. On the other hand, the increase of the third component may point to a slowing down of diffusional motion at the interface, although other effects, may play a role, which are discussed.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Aqueous Solvation Dynamics at Metal Oxide Surfaces

et al. 2006

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“…At long times the signal shows a monotonic decay; in the first OKE investigations it was interpreted as a bi-exponential relaxation, due to single molecule orientational dynamics 27 . Further experiments, extending the temperature range to the supercooled phase, proved that the slow decay follows a stretched exponential function, typical of structural relaxation phenomena, with a critical slow down of the relaxation times 28 .…”

Section: Hd-oke Water Datamentioning

confidence: 99%

Optical Kerr effect of liquid and supercooled water: The experimental and data analysis perspective

Taschin¹,

Bartolini²,

Eramo³

et al. 2014

The Journal of Chemical Physics

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The time-resolved optical Kerr effect spectroscopy (OKE) is a powerful experimental tool enabling accurate investigations of the dynamic phenomena in molecular liquids. We introduced innovative experimental and fitting procedures, that permit a safe deconvolution of sample response function from the instrumental function. This is a critical issue in order to measure the dynamics of sample presenting weak signal, e.g. liquid water. We report OKE data on water measuring intermolecular vibrations and the structural relaxation processes in an extended temperature range, inclusive of the supercooled states. The unpreceded data quality makes possible a solid comparison with few theoretical models; the multi-mode Brownian oscillator model, the Kubo's discrete random jump model and the schematic mode-coupling model. All these models produce reasonable good fits of the OKE data of stable liquid water, i.e. over the freezing point. The features of water dynamics in the OKE data becomes unambiguous only at lower temperatures, i.e. for water in the metastable supercooled phase. Hence this data enable a valid comparison between the model fits. We found that the schematic mode-coupling model provides the more rigorous and complete model for water dynamics, even if is intrinsic hydrodynamic approach hide the molecular informations.

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“…Apart from overdamped and diffusive contributions [28], it essentially consists of three broad intermolecular vibrational bands originating from the three quasi-degenerate restricted rotational modes (i.e. librations) and the two restricted translational degrees of freedom that are directed parallel and perpendicular to H-bonds between nearest neighbor molecules [26,27]. Thus, the phonon spectral density of liquid water has substantial amplitude up to about 1000 cm −1 extending almost into the intramolecular vibrational region.…”

Section: Introductionmentioning

confidence: 99%

“…The phonon-spectral density of liquid water is highly unique due to the existence of the extended random H-bond network [26,27]. Apart from overdamped and diffusive contributions [28], it essentially consists of three broad intermolecular vibrational bands originating from the three quasi-degenerate restricted rotational modes (i.e.…”

Section: Introductionmentioning

confidence: 99%

OH and NH Stretching Vibrational Relaxation of Liquid Ethanolamine

Knop

Lindner

Vöhringer³

2011

Zeitschrift Für Physikalische Chemie

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Vibrational Relaxation / Liquid Dynamics / Hydrogen-Bonding / Ultrafast SpectroscopyFemtosecond mid-infrared pump-probe spectroscopy was carried out to obtain information about the dynamics of vibrational energy relaxation in liquid ethanolamine at room temperature and ambient pressure. Through partial deuteration it was possible to disentangle the dynamics resulting from the OH and the NH stretching modes that proceed independently and simultaneously in the hydrogen-bonded liquid following an ultrafast vibrational excitation by a resonant mid-infrared pulse. The OH-stretching vibrational lifetime was determined to be 450 fs while the NH-stretching lifetime was found to be 1.2 ps. This large difference in lifetimes highlights the importance of the hydrogen-donating and the hydrogen-accepting character of the vibrating groups that are engaged in hydrogen-bonding.

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Ultrafast Raman-induced Kerr-effect of water: Single molecule versus collective motions

Abstract: Articles you may be interested in Low-frequency collective dynamics in deep eutectic solvents of acetamide and electrolytes: A femtosecond Raman-induced Kerr effect spectroscopic study

Cited by 138 publications

References 52 publications

Aqueous Solvation Dynamics at Metal Oxide Surfaces

Aqueous Solvation Dynamics at Metal Oxide Surfaces

Optical Kerr effect of liquid and supercooled water: The experimental and data analysis perspective

OH and NH Stretching Vibrational Relaxation of Liquid Ethanolamine

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