Transient absorption of vibrationally excited water

Bakker, H. J.; Nienhuys, Han-Kwang; Gallot, Guilhem; Lascoux, N.; Gale, G. M.; Leicknam, J.-Cl.; Bratos, S.

doi:10.1063/1.1432687

Cited by 71 publications

(81 citation statements)

References 39 publications

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“…Bakker and co-workers used the same Lippincott-Schroeder model with the same set of parameters when they concluded that it cannot explain the asymmetry in linewidth. 39 However, they argued in terms of a classical distribution of O· · ·O distances, which for ice Ih is too small to explain the effect (in contrast to liquid water 50,51 ). In essence, it is the quantum-mechanical delocalization of the wavefunction in the R O···O direction (Fig.…”

Section: Discussionmentioning

confidence: 98%

“…[59][60][61][62] Also in liquid water, the 1-2 transition is broader than the 0-1 transition, and in fact it has been argued that this reflects the anharmonic coupling to the O· · ·O hydrogen the bond length. 50,51 However, due to the much larger effect of disorder in water, this effect is largely blurred. Hence it appears that ice Ih is better suited to study the quantum-mechanical character of the hydrogen bond and its consequence for vibrational spectroscopy.…”

Section: Discussionmentioning

confidence: 99%

“…43, 44 Bakker and co-workers have extended the idea and applied it to pump-probe spectroscopy, which, in essence, includes higher vibrational states. They explain successfully the asymmetry of the spectral width of the 0-1 versus the 1-2 transition in the IR-pump-probe response in liquid water, 50,51 but conclude that it fails for ice Ih, 39 where this asymmetry is much more pronounced but structural disorder is less. We show here that we can in fact explain the 2D IR response of both the OH vibration of HOD/D 2 O and the OD vibration of HOD/H 2 O, when taking into account non-adiabatic couplings within the Lippincott-Schroeder potential.…”

Section: Theorymentioning

confidence: 97%

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Two-dimensional infrared spectroscopy of isotope-diluted ice Ih

Perakis

Widmer

Hamm

2011

The Journal of Chemical Physics

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We present experimental 2D IR spectra of isotope diluted ice Ih (i.e., the OH stretch mode of HOD in D2O and the OD stretch mode of HOD in H2O) at T = 80 K. The main spectral features are the extremely broad 1-2 excited state transition, much broader than the corresponding 0-1 groundstate transition, as well as the presence of quantum beats. We do not observe any inhomogeneous broadening that might be expected due to proton disorder in ice Ih. Complementary, we perform simulations in the framework of the Lippincott-Schroeder model, which qualitatively reproduce the experimental observations. We conclude that the origin of the observed line shape features is the coupling of the OH-vibrational coordinate with crystal phonons and explain the beatings as a coherent oscillation of the O⋅⋅⋅O hydrogen bond degree of freedom.

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Section: Discussionmentioning

confidence: 98%

Section: Discussionmentioning

confidence: 99%

Section: Theorymentioning

confidence: 97%

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Two-dimensional infrared spectroscopy of isotope-diluted ice Ih

Perakis

Widmer

Hamm

2011

The Journal of Chemical Physics

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“…14 Bulk water dynamics occur over a range of time scales, from tens of femtoseconds to several picoseconds. [15][16][17][18][19][20][21][22] These dynamics are complex and encompass elastic and inelastic interactions with the surrounding water molecules. Vibrational lifetimes, excitation transfer, dephasing and orientational correlation times are all observed to decay by ∼2 ps for bulk water.…”

Section: Introductionmentioning

confidence: 99%

Dynamics of Nanoscopic Water: Vibrational Echo and Infrared Pump−Probe Studies of Reverse Micelles

2005

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The dynamics of water in nanoscopic pools 1.7-4.0 nm in diameter in AOT reverse micelles were studied with ultrafast infrared spectrally resolved stimulated vibrational echo and pump-probe spectroscopies. The experiments were conducted on the OD hydroxyl stretch of low-concentration HOD in the H 2 O, providing a direct examination of the hydrogen-bond network dynamics. Pump-probe experiments show that the vibrational lifetime of the OD stretch mode increases as the size of the reverse micelle decreases. These experiments are also sensitive to hydrogen-bond dissociation and reformation dynamics, which are observed to change with reverse micelle size. Spectrally resolved vibrational echo data were obtained at several frequencies. The vibrational echo data are compared to data taken on bulk water and on a 6 M NaCl solution, which is used to examine the role of ionic strength on the water dynamics in reverse micelles. Two types of vibrational echo measurements are presented: the vibrational echo decays and the vibrational echo peak shifts. As the water nanopool size decreases, the vibrational echo decays become slower. Even the largest nanopool (4 nm, ∼1000 water molecules) has dynamics that are substantially slower than bulk water. It is demonstrated that the slow dynamics in the reverse micelle water nanopools are a result of confinement rather than ionic strength. The data are fit using time-dependent diagrammatic perturbation theory to obtain the frequency-frequency correlation function (FFCF) for each reverse micelle. The results are compared to the FFCF of water and show that the largest differences are in the slowest time scale dynamics. In bulk water, the slowest time scale dynamics are caused by hydrogen-bond network equilibration, i.e., the making and breaking of hydrogen bonds. For the smallest nanopools, the longest time scale component of the water dynamics is ∼10 times longer than the dynamics in bulk water. The vibrational echo data for the smallest reverse micelle displays a dependence on the detection wavelength, which may indicate that multiple ensembles of water molecules are being observed.

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“…Over the last decades, this notion has motivated a lot of work on the dynamical properties of bulk liquid water (1)(2)(3)(4)(5)(6)(7). However, the role of water in (bio)chemical processes is often played by a limited number of water molecules in a strongly restricted molecular environment.…”

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confidence: 99%

Dynamics of confined water molecules

Gilijamse

Lock

Bakker

2005

Proc. Natl. Acad. Sci. U.S.A.

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We present femtosecond midinfrared pump-probe measurements of the molecular motion and energy-transfer dynamics of a water molecule that is enclosed by acetone molecules. These confined water molecules show hydrogen-bond and orientational dynamics that are much slower than in bulk liquid water. This behavior is surprising because the hydrogen bonds to the CAO groups of the acetone molecules are weaker than the hydrogen bonds in bulk water. The energy transfer between the OOH groups of the confined water molecules has a time constant of 1.3 ؎ 0.2 ps, which is >20 times slower than in bulk water. We find that this energy transfer is governed completely by the rate at which hydrogen bonds are broken and reformed, and we identify the short-lived molecular complex that forms the transition state of this process.hydrogen bonding ͉ infrared pump-probe spectroscopy ͉ energy transfer W ater plays an essential role in many chemical and biological processes. Over the last decades, this notion has motivated a lot of work on the dynamical properties of bulk liquid water (1-7). However, the role of water in (bio)chemical processes is often played by a limited number of water molecules in a strongly restricted molecular environment. For example, the stability, structure, and biological function of proteins are largely determined by only a few surrounding layers of water molecules (8). When the water molecules participate directly in a reaction, the number of involved water molecules is even smaller. For example, the proton-pumping function of bacteriorhodopsin involves changes of the hydrogen network that is formed by particular amino acids of the protein and only a few confined water molecules (9-12).Recently, the dynamics of water in restricted environments was studied by comparing the spectral dynamics of an optically excited probe molecule embedded in a hydrated (bio)molecule with the spectral dynamics of the same probe molecule in bulk water (13). The spectral dynamics reflect the collective rearrangement of the solvating water, and were found to be much slower within the hydrated (bio)molecule than in bulk water. In this article, we present a study of the hydrogen-bond and energy-transfer dynamics of individual H 2 O and 1 H 2 HO molecules in a confined environment. In this study, we probed the dynamics of the water molecules directly with femtosecond midinfrared laser pulses that are resonant with the OOH stretch vibrations. Experimental MethodsThe system of confined water molecules is prepared by dissolving water (0.4 mol͞liter) in a mixture of acetone (4.0 mol͞liter) and CCl 4 . The structures that are formed in this mixture have a polar internal part consisting of an enclosed water molecule forming hydrogen bonds to the CAO groups of a few surrounding acetone molecules, and an apolar external part formed by the methyl groups of the acetone molecules. The favorable interaction between the methyl groups and the CCl 4 molecules allows these structures to enter the apolar CCl 4 matrix. The molecular ratio of H 2 O͞aceton...

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Transient absorption of vibrationally excited water

Cited by 71 publications

References 39 publications

Two-dimensional infrared spectroscopy of isotope-diluted ice Ih

Two-dimensional infrared spectroscopy of isotope-diluted ice Ih

Dynamics of Nanoscopic Water: Vibrational Echo and Infrared Pump−Probe Studies of Reverse Micelles

Dynamics of confined water molecules

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