Hidden Isolated OH at the Charged Hydrophobic Interface Revealed by Two‐Dimensional Heterodyne‐Detected VSFG Spectroscopy

Ahmed, Mohammed; Inoue, Ken; Nihonyanagi, Satoshi; Tahara, Tahei

doi:10.1002/anie.202002368

Cited by 12 publications

(12 citation statements)

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“…Heterodyne SFG spectroscopy at the water–air interface by Tahara and co-workers, demonstrated that the interference of O–H contributions with C–H and nonresonant contributions strongly depends on the orientation of interfacial water . As a consequence, for the homodyne SFG spectra in our work, the interference condition of ν(OH) bands with χ NR (2) depends on the relative phase and thus the net molecular orientation of interfacial water molecules as well, which can influence the shape of the SFG spectra in Figure .…”

mentioning

confidence: 48%

Potential-Induced Adsorption and Structuring of Water at the Pt(111) Electrode Surface in Contact with an Ionic Liquid

Kemna

Braunschweig

2020

J. Phys. Chem. Lett.

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Water adsorption is important in many fields from surface electrochemistry to electrocatalysis, where molecular-level information is much needed in order to gain a detailed understanding of the role of interfacial water. Here we report on water at Pt(111) surfaces in contact with an [EIMIM][BF4] ionic liquid, which was spectroscopically resolved by using in situ sum-frequency generation (SFG). O–H modes are used to study water adsorption and water structure as a function of electrode potential, while the analysis of C–H modes is used to infer orientational changes of [EMIM] cations at the interface. Different from the bulk where free water molecules are found, SFG spectra provide evidence that an interfacial layer with an extended network of hydrogen-bonded water molecules exists and grows with increasing absolute potential which is used to identify the potential of zero charge at +0.1 V SHE, where a pronounced minimum in O–H intensity is found.

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mentioning

confidence: 48%

Potential-Induced Adsorption and Structuring of Water at the Pt(111) Electrode Surface in Contact with an Ionic Liquid

Kemna

Braunschweig

2020

J. Phys. Chem. Lett.

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“…A positive charge typically aligns the water dipole, lined up with the bisector of the two OH bonds within the water molecule, as has previously been shown for water hydrating ions 162 . Yet, a negative charge can also act as an H-bond acceptor, aligning only one of the OH bonds, rather than the dipole of the water molecules 163,164 .…”

Section: Water Structuring and Orientationmentioning

confidence: 99%

“…To this point, we have addressed the classical mean-field theories of charged aqueous interfaces, discussed each component of the system and pointed out several observations that suggest that this classical description is qualitatively incomplete. Along with the development of in situ experimental techniques that allow looking at the water-ion-charged interface in more (sometimes even atomic) detail 55,91,144,146,154,164,189,194,195 , simulations have allowed the study of the breakdown of the classical mean-field theories at the molecular length scale. This has led to the successful development of modified mean-field approaches.…”

Section: Modern Electrical Double Layer Theoriesmentioning

confidence: 99%

Water at charged interfaces

et al. 2021

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The ubiquity of aqueous solutions in contact with charged surfaces and the realization that the molecular-level details of water-surface interactions often determine interfacial functions and properties relevant in many natural processes have led to intensive research. Even so, many open questions remain regarding the molecular picture of the interfacial organization and preferential alignment of water molecules, as well as the structure of water molecules and ion distributions at different charged interfaces. While water, solutes and charge are present in each of these systems, the substrate can range from living tissues to metals. This diversity in substrates has led to different communities considering each of these types of aqueous interface. In this Review, by considering water in contact with metals, oxides and biomembranes, we show the essential similarity of these disparate systems. While in each case the classical mean-field theories can explain many macroscopic and mesoscopic observations, it soon becomes apparent that such theories fail to explain phenomena for which molecular properties are relevant, such as interfacial chemical conversion. We highlight the current knowledge and limitations in our understanding and end with a view towards future opportunities in the field.

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“…Vibrational sum frequency generation (VSFG) spectroscopy has intrinsic interface selectivity and has been extensively employed to study interfacial water. , To elucidate the structure − and dynamics − of water at various interfaces, most of the prior VSFG studies have examined the OH stretch vibration of the water. This is because of the strong intensity of the OH stretch band and the high sensitivity of the OH stretch frequency to the hydrogen-bond strength of water.…”

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confidence: 99%

Resolving the Controversy over Dipole versus Quadrupole Mechanism of Bend Vibration of Water in Vibrational Sum Frequency Generation Spectra

Ahmed

Nihonyanagi

Kundu

et al. 2020

J. Phys. Chem. Lett.

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Recently, there has been controversy over whether the HOH bend signal of water in the vibrational sum frequency generation (VSFG) spectrum arises from the conventional dipole mechanism or the quadrupole mechanism. Here, we show that the Im χ (2) (the imaginary part of the second-order nonlinear susceptibility) spectra of the HOH bend mode of water at oppositely charged monolayer/water interfaces all exhibit positive bands, irrespective of the difference in the sign of the charge at the interface. Furthermore, it is found that the peak frequency of the HOH bend band substantially changes depending on the chemical structure of the charged headgroup located at the interface. These results demonstrate that the VSFG signal of the HOH bend vibration is generated from interfacial water with the interfacial quadrupole mechanism that is associated with the large field gradient of incident lights localized in a very thin region at the interface.

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Hidden Isolated OH at the Charged Hydrophobic Interface Revealed by Two‐Dimensional Heterodyne‐Detected VSFG Spectroscopy

Cited by 12 publications

References 74 publications

Potential-Induced Adsorption and Structuring of Water at the Pt(111) Electrode Surface in Contact with an Ionic Liquid

Potential-Induced Adsorption and Structuring of Water at the Pt(111) Electrode Surface in Contact with an Ionic Liquid

Water at charged interfaces

Resolving the Controversy over Dipole versus Quadrupole Mechanism of Bend Vibration of Water in Vibrational Sum Frequency Generation Spectra

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