Dynamics of water probed with vibrational echo correlation spectroscopy

Asbury, John B.; Steinel, Tobias; Kwak, Kyungwon; Corcelli, Steven A.; Lawrence, C. P.; Skinner, James; Fayer, M. D.

doi:10.1063/1.1818107

Cited by 355 publications

(592 citation statements)

References 70 publications

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“…Table 1 contains the vibrational lifetimes (T 1 ) for the three reverse micelles, bulk water, and the NaCl solution. In hydrogen-bonded liquids, the vibrational lifetime is not trivial to measure, because the pump-probe experiment can be sensitive to spectral dynamics in the ground and excited state 62 and hydrogen bond dissociation, 69,78,79 in addition to vibrational relaxation. If a frequency-selected subset of the water molecules is excited by a relatively narrow pump pulse, then spectral diffusion in the ground and excited state will produce a frequency-dependent signal.…”

Section: Resultsmentioning

confidence: 99%

“…In addition to the data shown in Figure 2, data were taken at a wavelength 160 cm -1 to the red of the absorption maximum of each sample. The wavelength of 160 cm -1 is the anharmonicity of the OD stretch of HOD in water, 69 which is assumed to be the same for OD in the reverse micelles. Similar to that for bulk water, pump-probe decays measured at the peak of the 0-1 transition display a long-lived component that lasts for tens of picoseconds.…”

Section: Resultsmentioning

confidence: 99%

“…The analysis gives the FFCFs for the different-sized water nanopools, which is compared to the FFCF obtained for bulk water. 69 The results show that even the largest nanopools studied have dynamics that are substantially different from bulk water and that the differences are not attributable to ionic strength. Analysis of the frequency dependence of the vibrational echo signals suggests that the dynamics in the smallest reverse micelles involve more than one subensemble of water molecules.…”

Section: Introductionmentioning

confidence: 81%

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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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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 81%

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

2005

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“…Nonlinear vibrational spectroscopy, such as two dimensional infrared spectroscopy (2D IR) [26][27][28][29][30][31][32][33], is an excellent tool to monitor the local structure and dynamical properties of the hydrogen bonds in water. These experiments make use of the fact that the vibrational frequency of the OH stretch vibration is highly correlated with the OO distance of a pair of hydrogen bonded water molecules [34][35][36][37][38].…”

Section: Introductionmentioning

confidence: 99%

Two-Dimensional Infrared Spectroscopy of Isotope-Diluted Low Density Amorphous Ice

2013

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We present two-dimensional (2D) infrared (IR) spectra of isotope diluted ice in its low density amorphous form. Amorphous ice, which is structurally more similar to liquid water than to crystalline ice, provides higher resolution spectra of the hydrogen bond potentials because all motion is frozen. In the case of OD vibration of HOD in H2O, diagonal and off-diagonal (intermode) anharmonicity as well as the relaxation rate of the first excited state increase with hydrogen bond strength in a consistent way. For the OH vibration of HOD in D2O, additional more specific couplings need to be taken into account to explain the 2D IR response, that is, a Fermi resonance with the HOD bend vibration and couplings to phonon modes that lead to quantum beating. The lifetime of the fist excited state, 240 fs, is the shortest ever reported for any phase of isotope diluted water. We present 2D IR spectra of isotope diluted ice in its low density amorphous form. Amorphous ice, which is structurally more similar to liquid water than to crystalline ice, provides higher resolution spectra of the hydrogen bond potentials because all motion is frozen. In the case of OD vibration of HOD in H2O, diagonal and off-diagonal (inter-mode) anharmonicity as well as the relaxation rate of the first excited state increases with hydrogen bond strength in a consistent way. For the OH vibration of HOD in D2O, additional more specific couplings need to be taken into account to explain the 2D IR response, that is, a Fermi resonance with the HOD bend vibration and couplings to phonon modes that lead to quantum beating. The lifetime of the fist excited state, 240 fs, is the shortest ever reported for any phase of isotope diluted water.

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“…2D IR experiments can also be useful as a tool for chemical structural analysis by revealing the relationship among different mechanical degrees of freedom of a molecular or biomolecular system. 2D IR vibrational echo experiments have been successfully applied to study fast chemical exchange reactions and solution dynamics, 29,31,36 water dynamics, 37,38 hydrogen network evolution, 28 intramolecular vibrational energy relaxations, 34 protein structures and dynamics, 30,39,40 and mixed chemicals analysis. 41 Since the first fast condensed matter vibrational echo experiments in 1993, 20 the field has advanced a great deal.…”

Section: Introductionmentioning

confidence: 99%

Probing dynamics of complex molecular systems with ultrafast 2D IR vibrational echo spectroscopy

Finkelstein

Zheng

Ishikawa

et al. 2007

Phys. Chem. Chem. Phys.

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148

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Ultrafast 2D IR vibrational echo spectroscopy is described and a number of experimental examples are given. Details of the experimental method including the pulse sequence, heterodyne detection, and determination of the absorptive component of the 2D spectrum are outlined. As an initial example, the 2D spectrum of the stretching mode of CO bound to the protein myoglobin (MbCO) is presented. The time dependence of the 2D spectrum of MbCO, which is caused by protein structural evolution, is presented and its relationship to the frequency-frequency correlation function is described and used to make protein structural assignments based on comparisons to molecular dynamics simulations. The 2D vibrational echo experiments on the protein horseradish peroxidase are presented. The time dependence of the 2D spectra of the enzyme in the free form and with a substrate bound at the active site are compared and used to examine the influence of substrate binding on the protein's structural dynamics. The application of 2D vibrational echo spectroscopy to the study of chemical exchange under thermal equilibrium conditions is described. 2D vibrational echo chemical exchange spectroscopy is applied to the study of formation and dissociation of organic solute-solvent complexes and to the isomerization around a carbon-carbon single bond of an ethane derivative.

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Dynamics of water probed with vibrational echo correlation spectroscopy

Cited by 355 publications

References 70 publications

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

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

Two-Dimensional Infrared Spectroscopy of Isotope-Diluted Low Density Amorphous Ice

Probing dynamics of complex molecular systems with ultrafast 2D IR vibrational echo spectroscopy

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