Hydroxide anion at the air–water interface

Mundy, Christopher J.; Kuo, I‐Feng W.; Tuckerman, Mark E.; Lee, Hee-Seung; Tobias, Douglas J.

doi:10.1016/j.cplett.2009.09.003

Cited by 119 publications

(124 citation statements)

References 48 publications

Supporting

Mentioning

115

Contrasting

Order By: Relevance

“…The type and hierarchy of the interactions (electrostatic, inductive, hydrogen bonding, and dispersive interactions) responsible for driving OH − to the interface are not fully resolved by current density functionals (7,44,(49)(50)(51)(52). balance each other on the aerial side of water, the point of zero charge, is pH PZC ∼3.…”

Section: Quantum-mechanical Calculationsmentioning

confidence: 99%

“…Some surface-specific nonlinear spectroscopic studies (9, 61), most theoretical calculations (7,51,62), and the ion partitioning analysis of surface tension data on electrolyte solutions (19) have predicted the accumulation of H 3 O + at and the exclusion of OH − from the air-water interface. On the basis of such evidence it has been argued that water surface is acidic (7,25).…”

Section: Quantum-mechanical Calculationsmentioning

confidence: 99%

See 1 more Smart Citation

Brønsted basicity of the air–water interface

Mishra

Enami

Nielsen

et al. 2012

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

167

201

View full text Add to dashboard Cite

Differences in the extent of protonation of functional groups lying on either side of water-hydrophobe interfaces are deemed essential to enzymatic catalysis, molecular recognition, bioenergetic transduction, and atmospheric aerosol-gas exchanges. The sign and range of such differences, however, remain conjectural. Herein we report experiments showing that gaseous carboxylic acids RCOOH(g) begin to deprotonate on the surface of water significantly more acidic than that supporting the dissociation of dissolved acids RCOOH(aq). Thermodynamic analysis indicates that > 6 H 2 O molecules must participate in the deprotonation of RCOOH(g) on water, but quantum mechanical calculations on a model air-water interface predict that such event is hindered by a significant kinetic barrier unless OH − ions are present therein. Thus, by detecting RCOO − we demonstrate the presence of OH − on the aerial side of on pH > 2 water exposed to RCOOH(g). Furthermore, because in similar experiments the base (Me) 3 N(g) is protonated only on pH < 4 water, we infer that the outer surface of water is Brønsted neutral at pH ∼3 (rather than at pH 7 as bulk water), a value that matches the isoelectric point of bubbles and oil droplets in independent electrophoretic experiments. The OH − densities sensed by RCOOH(g) on the aerial surface of water, however, are considerably smaller than those at the (>1 nm) deeper shear planes probed in electrophoresis, thereby implying the existence of OH − gradients in the interfacial region. This fact could account for the weak OH − signals detected by surface-specific spectroscopies.gas-liquid reactions | surface potential | water surface acidity | interfacial proton transfer A cid-base chemistry at aqueous interfaces lies at the heart of major processes in chemistry and biology. Changes in the degree of dissociation of the acidic/basic residues upon translocation between aqueous and hydrophobic microenvironments orchestrate enzyme catalysis (1), drive proton/electron transport across biomembranes (2, 3), and mediate molecular recognition and self-assembly phenomena (4-6). Despite its importance, the characterization of acid-base chemistry at aqueous interfaces remains fraught with uncertainties (7-11). Basic questions linger about the thickness of interfacial layers (12), how acidity changes through the interfacial region (13), and the mechanistic differences between proton transfer (PT) across interfacial (IF) versus in bulk (B) water (10,14). Because aqueous surfaces are usually charged relative to the bulk liquid (15), the thermodynamic requirement of uniform electrochemical activity throughout (including the interfacial regions) implies that the chemical activity of protons (pH) in IF could be different from that in the B liquid. Reduced hydration of ionic species at the interface could force acids and bases toward their undissociated forms (16).These fundamental issues have been extensively investigated via electrostatic (17) and electrokinetic experiments (11), surface tension studies and analysis (1...

show abstract

Section: Quantum-mechanical Calculationsmentioning

confidence: 99%

Section: Quantum-mechanical Calculationsmentioning

confidence: 99%

Brønsted basicity of the air–water interface

Mishra

Enami

Nielsen

et al. 2012

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

167

201

View full text Add to dashboard Cite

show abstract

“…For example, the involvement of an O-H(D) oscillator in an intra-or intermolecular hydrogen bond has been often judged by the direction of the shift in the O-H(D) stretching frequency. The magnitude of this shift, on the other hand, has often been found to be proportional to the interaction strength [10][11][12][13][14][15][16][17]20]. Besides the effect of noncovalent interactions on the static and dynamical properties of the intramolecular O-H(D) oscillators, also the influence of incrystal (or external) electrostatic fields on the statics and dynamics of the O-H(D) oscillators has been thoroughly addressed [21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

“…The dynamics of hydrogen bond forming and breaking within liquid water is a subject of continual research interests. Behavior of the essential products of water autoprotolysis process, the H 3 O + and OH -ionic species, has also been a subject of continuing debates in the literature [10][11][12][13][14][15][16][17]. Even very essential issues, such as the ability of the OH -ions to act as hydrogenbond proton donors in bulk water, have been addressed from various viewpoints [10][11][12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Low Bending Vibrations of Crystalline Water Molecules: An Ongoing Quest or a Final Word – Topical Review – A Tribute to Academician Bojan Šoptrajanov

Pejov¹,

Jovanovski²

2017

Contributions

View full text Add to dashboard Cite

The main aim of this topical review is to provide a concise but yet complete overview of the research that has been done in the field of low-lying crystalline water bending vibrations. Both theoretical and experimental work in the field is reviewed, and the most important dilemmas and obstacles hampering a direct explanation of the phenomenon are outlined. The present status in this field is also overviewed and clarified. While this topical review has mostly been focused on crystalline water molecules in crystalline hydrates and their vibrational properties, also some other interesting and exciting systems that have recently attracted the attention of the scientific community are covered. These included water absorbed on surfaces as well as water at the air-water interfaces.

show abstract

“…264,[295][296][297][298][299][300][301] Experimental and theoretical work has established that the concentration of hydronium cations is enhanced at the water liquid/vapor interface compared with the bulk.…”

Section: The Potential Of Mean Force-applicationsmentioning

confidence: 99%

Reactivity and Dynamics at Liquid Interfaces

Benjamin¹

2015

Reviews in Computational Chemistry

View full text Add to dashboard Cite

Hydroxide anion at the air–water interface

Cited by 119 publications

References 48 publications

Brønsted basicity of the air–water interface

Brønsted basicity of the air–water interface

Low Bending Vibrations of Crystalline Water Molecules: An Ongoing Quest or a Final Word – Topical Review – A Tribute to Academician Bojan Šoptrajanov

Reactivity and Dynamics at Liquid Interfaces

Contact Info

Product

Resources

About