Dynamics of Local Substructures in Water Observed by Ultrafast Infrared Hole Burning

Laenen, R.; Rauscher, C.; Laubereau, A.

doi:10.1103/physrevlett.80.2622

Cited by 271 publications

(331 citation statements)

References 17 publications

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“…14,16,31,33,34 Usually, a model is invoked that comprises wavelength-dependent dynamic parameters such as vibrational relaxation and spectral diffusion to reproduce the data. 14,33,35 The lifetime of the OH vibration in D 2 O has been reported to be in the range of 0.7- 16 While a shift of the hydroxyl stretch band is found in all these experiments, the production of photoproducts has not been included in the analysis of these experiments, although it has been considered in an echo peak shift experiment on HOD in D 2 O 25 and experiments on methanol. 17…”

Section: Introductionmentioning

confidence: 99%

Watching Hydrogen Bonds Break: A Transient Absorption Study of Water

et al. 2004

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Ultrafast infrared transient absorption measurements of the complete hydroxyl OD stretching mode spectrum of HOD in water, from 100 fs to tens of picoseconds, observe hydrogen bond breaking and monitor the equilibration of the hydrogen bond network in water. In addition, the vibrational lifetime, the time constant for hydrogen bond breaking, and the rate of orientational relaxation are determined. The reactant and photoproduct spectra of the hydrogen bond breaking process are identified by decomposing the transient spectra into two components, the initial spectrum associated with vibrational excited states (reactants) and the long-time spectrum associated with broken hydrogen bonds (photoproducts). By properly taking into account the perturbation of the reactant spectrum decay by the growth of the photoproduct spectrum, it is found that the vibrational relaxation (1.45 ps) and orientational relaxation (1.53 ps) are wavelength independent and, therefore, independent of the degree of hydrogen bonding. Energy deposited into water by vibrational relaxation does not immediately break a hydrogen bond by predissociation nor produce a thermally equilibrated hydrogen bond distribution at an elevated temperature. Following deposition of energy by vibrational relaxation, the hydrogen bond breaking time is 800 fs, and there is a transient period of several picoseconds during which the hydrogen bond distribution is not in thermal equilibrium.

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Section: Introductionmentioning

confidence: 99%

Watching Hydrogen Bonds Break: A Transient Absorption Study of Water

et al. 2004

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“…The vibrational properties of liquid water have received considerable attention. [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22]31,[43][44][45] Much experimental [9][10][11][12][13][14][15][16][17] and theoretical [18][19][20][21]43,44 effort has focused on the OH stretch of HOD in D 2 O. This is a simpler system than neat water since that mode is spectrally isolated so that the rapid resonant intermolecular vibrational energy transfer 46 is eliminated.…”

Section: Introductionmentioning

confidence: 99%

Collective Solvent Coordinates for the Infrared Spectrum of HOD in D₂O Based on an ab Initio Electrostatic Map

et al. 2004

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An ab initio MP2 vibrational Hamiltonian of HOD in an external electrostatic potential parametrized by the electric field and its gradient-tensor is constructed. By combining it with the fluctuating electric field induced by the D 2 O solvent obtained from molecular dynamics simulations, we calculate the infrared absorption of the O-H stretch. The resulting solvent shift and infrared line shape for three force fields (TIP4P, SPC/E, and SW) are in good agreement with the experiment. A collective coordinate response for the solvent effect is constructed by identifying the main electrostatic field and gradient components contributing to the line shape. This allows a realistic stochastic Liouville equation simulation of the line shapes which is not restricted to Gaussian frequency fluctuations.

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“…1b), whereas they vary with respect to the sign of their coherence states. In analogy to the 2D-IR case, these diagrams oscillate with (ω 1 , ω 3 , ω 5 ) = (±ω 01 , ±ω 01 , ω 01 ), depending on whether they are in a |0⟩⟨1| or in a |1⟩⟨0| coherence state during t 1 and t 3 . With respect to the sequence of states during the population times, there are ten possibilities in 3D-IR spectroscopy, labeled I-X in Fig.…”

Section: Introductionmentioning

confidence: 99%

“…In the mid-IR range, the OH stretch vibration is typically used to probe the local hydrogen bonding environment. The vibrational relaxation of water has been experimentally investigated by numerous pump-probe studies [1][2][3][4][5][6][7][8][9] assisted by simulations [10][11][12], whereas the hydrogen bond exchange dynamics have been captured by photon echo and 2D-IR spectroscopy of both neat [13,14] and isotope diluted water [15][16][17][18][19][20][21] (see also the reviews [22][23][24][25][26]). Isotope dilution significantly simplifies the problem, as one can resonantly excite the OD stretch mode without exciting the OH oscillators surrounding the isolated HOD molecule.…”

Section: Introductionmentioning

confidence: 99%

Three-dimensional infrared spectroscopy of isotope-diluted ice Ih

Perakis

Widmer

Hamm

2013

The Journal of Chemical Physics

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Using three-dimensional infrared (3D-IR) spectroscopy, we investigate the vibrational dynamics of isotope-diluted ice Ih. By probing the OD stretch mode of HOD in H2O, we observe an extremely rapid decay ( 200 fs) of the population from the second vibrational excited state. Quantum simulations based on a two-dimensional Lippincott-Schroeder potential agree nearly quantitatively with the experimental 3D-IR lineshapes and dynamics. The model suggests that energy dissipation is enhanced due to nonadiabatic effects between vibrational states, which arise from strong mode-mixing between the OD stretch mode with lattice degrees of freedom. Furthermore, we compare the simulation results to ab-initio based potentials, in which the hydrogen bond anharmonicity is too small to reproduce the experimental 3D-IR spectra. We thus conclude that the Lippincott-Schroeder potential effectively coalesces many degrees of freedom of the crystal into one intermolecular coordinate. Three-dimensional infrared spectroscopy of isotope-diluted ice IhFivos Perakis, Joanna A. Borek and Peter Hamm Physikalisch-Chemisches Institut, Universität Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland, phamm@pci.uzh.ch (Dated: June 14, 2013) Using three-dimensional infrared (3D-IR) spectroscopy, we investigate the vibrational dynamics of isotope-diluted ice Ih. By probing the OD stretch mode of HOD in H2O, we observe an extremely rapid decay (≈200 fs) of the population from the second vibrational excited state. Quantum simulations based on a two-dimensional Lippincott-Schroeder potential agree nearly quantitatively with the experimental 3D-IR lineshapes and dynamics. The model suggests that energy dissipation is enhanced due to nonadiabatic effects between vibrational states, which arise from strong mode-mixing between the OD stretch mode with lattice degrees of freedom. Furthermore, we compare the simulation results to ab-initio based potentials, in which the hydrogen bond anharmonicity is too small to reproduce the experimental 3D-IR spectra. We thus conclude that the Lippincott-Schroeder potential effectively coalesces many degrees of freedom of the crystal into one intermolecular coordinate.

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Dynamics of Local Substructures in Water Observed by Ultrafast Infrared Hole Burning

Cited by 271 publications

References 17 publications

Watching Hydrogen Bonds Break: A Transient Absorption Study of Water

Watching Hydrogen Bonds Break: A Transient Absorption Study of Water

Collective Solvent Coordinates for the Infrared Spectrum of HOD in D₂O Based on an ab Initio Electrostatic Map

Three-dimensional infrared spectroscopy of isotope-diluted ice Ih

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Dynamics of Local Substructures in Water Observed by Ultrafast Infrared Hole Burning

Cited by 271 publications

References 17 publications

Watching Hydrogen Bonds Break: A Transient Absorption Study of Water

Watching Hydrogen Bonds Break: A Transient Absorption Study of Water

Collective Solvent Coordinates for the Infrared Spectrum of HOD in D2O Based on an ab Initio Electrostatic Map

Three-dimensional infrared spectroscopy of isotope-diluted ice Ih

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Product

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Collective Solvent Coordinates for the Infrared Spectrum of HOD in D₂O Based on an ab Initio Electrostatic Map