Sovago<i>et al.</i>Reply:

Sovago, Maria; Campen, R. Kramer; Wurpel, George W. H.; Müller, Markus; Bakker, Huib J.; Bonn, Mischa

doi:10.1103/physrevlett.101.139402

Cited by 115 publications

(228 citation statements)

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“…The two peaks appearing at ∼2350 and ∼2500 cm −1 have been assigned in different ways, to "ice-like" and "liquid-like" structures [3][4][5] and to the result of intra and intermolecular coupling. 14,18 There is surprising similarity between the two spectra, raising the question whether the interfacial water structure is also very similar. The spectra reported in Fig.…”

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confidence: 99%

“…2 Despite its importance for disciplines such as electrochemistry, atmospheric chemistry, and membrane biophysics, the structure of interfacial water has remained highly debated. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] The challenge of specifically probing molecules at the outermost surface layers of water has been overcome with sum-frequency generation (SFG) spectroscopy of the O-H stretch vibrations of the water molecules. In an SFG experiment, infrared and visible laser pulses are overlapped in space and time on the surface, and the sum-frequency of the two laser fields can be generated, but in the top molecular layers only.…”

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confidence: 99%

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Communication: Interfacial water structure revealed by ultrafast two-dimensional surface vibrational spectroscopy

Zhang

Piątkowski

Bakker

et al. 2011

The Journal of Chemical Physics

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Knowledge of the interfacial water structure is essential for a basic understanding of the many environmental, technological, and biophysical systems in which aqueous interfaces appear. Using ultrafast two-dimensional surface-specific vibrational spectroscopy we show that the structure of heavy water at the water-air interface displays short-lived heterogeneity and is very different from that at the water-lipid interface.

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confidence: 99%

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confidence: 99%

Communication: Interfacial water structure revealed by ultrafast two-dimensional surface vibrational spectroscopy

Zhang

Piątkowski

Bakker

et al. 2011

The Journal of Chemical Physics

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“…In earlier studies, SFG has been used to probe vibrational relaxation in molecules that have been IR-pumped to excited vibrational states in the ground electronic state. [51][52][53] SFG has also been used to great advantage in measuring the dynamics of vibrational energy transfer along a hydrocarbon chain. 54 In the present investigation, SFG is used to monitor the solvation dynamics of interfacial molecules.…”

Section: Introductionmentioning

confidence: 99%

Solvation Dynamics at the Air/Water Interface with Time-Resolved Sum-Frequency Generation

2010

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The dynamics of molecular solvation at the air/water interface has been monitored with femtosecond timeresolved pump-sum frequency generation (TR-SFG), a technique that has been shown to be feasible in the study of ultrafast rotional motions. In the work reported here, the solvation process was monitored by femtosecond photoexcitation of interfacial coumarin 314 (C314) molecules. In these experiments, the SFG signal is brought into a vibrational resonance with the carbonyl symmetric stretch of C314 by tuning the IR pulse to the carbonyl frequency by using a pump-TR-SFG probe. Two solvation time constants were obtained, 230 ( 40 fs and 2.17 ( 0.3 ps. These results are the same within experimental error as those measured in time-resolved second-harmonic generation (TR-SHG) experiments. This suggests that the solvent response is due to solvation-induced shifts of the electronic-state energies in the SFG hyperpolarizability and not significantly to solvation effects on the energy of the carbonyl vibration nor to the strength of the carbonyl vibrational transition moment. In addition, an explanation of the similar solvation dynamics of a newly created ion at the air/water interface and in bulk water, which is based on molecular-dynamics simulations (Benjamin, I. J. Chem. Phys. 1991, 95 (5), 3698-3709), could explain the similar solvation dynamics we found for C314. The physical description is that the first solvation shell is essentially the same in bulk water and at the air/water interface.

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“…In the context of vibrational spectroscopy of bulk liquid water, we have shown for simulated systems that a pronounced shoulder in the Raman line shape signifies nothing more than the nonlinear relationship between frequency and hydrogen bond geometry. [11] For liquid-vapor interfaces as well, distributions of r OH for hydrogen bonded species do not suggest a meaningful segregation into ice-like and liquid-like structures [51] as previously suggested. [50] By this measure only free OH species stand out as a discrete variation in intermolecular structure.…”

Section: Discussionmentioning

confidence: 60%

Toward a Simple Molecular Understanding of Sum Frequency Generation at Air−Water Interfaces

2009

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Second-order vibrational spectroscopies successfully isolate signals from interfaces, but they report on intermolecular structure in a complicated and indirect way. Here we adapt a perspective on vibrational response developed for bulk spectroscopies to explore the microscopic fluctuations to which sum frequency generation (SFG), a popular surface-specific measurement, is most sensitive.We focus exclusively on inhomogeneous broadening of spectral susceptibilities for OH stretching of HOD as a dilute solute in D 2 O. Exploiting a simple connection between vibrational frequency shifts and an electric field variable, we identify several functions of molecular orientation whose averages govern SFG. The frequency-dependence of these quantities is well captured by a pair of averages, involving alignment of OH and OD bonds with the surface normal at corresponding values of the electric field. The approximate form we obtain for SFG susceptibility highlights a dramatic sensitivity to the way a simulated liquid slab is partitioned for calculating second-order response.

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Sovagoet al.Reply:

Cited by 115 publications

References 4 publications

Communication: Interfacial water structure revealed by ultrafast two-dimensional surface vibrational spectroscopy

Communication: Interfacial water structure revealed by ultrafast two-dimensional surface vibrational spectroscopy

Solvation Dynamics at the Air/Water Interface with Time-Resolved Sum-Frequency Generation

Toward a Simple Molecular Understanding of Sum Frequency Generation at Air−Water Interfaces

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