Some fundamental properties and reactions of ice surfaces at low temperatures

Park, Seong-Chan; Moon, Eui-Seong; Kang, Heon

doi:10.1039/c003592k

Cited by 61 publications

(119 citation statements)

References 105 publications

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“…Both conditions favor the breaking of the second coordination shell of the proton and reduce the likeliness of PT. The comparison of the energy barriers for waterhydronium exchange (of the order of 10 kJ/mol) indicates a general good agreement with available experimental data of activation energies for PT [69][70][71][72] as well as with results previously reported by other authors on equivalent PMFs barriers for proton transfer in water using a different approach, based on the so-called dissociative water potential [42].…”

Section: Discussionsupporting

confidence: 74%

“…Experimental data revealed values of the order of -10 kJ/mol for the activation energy of PT at the surface of polycrystalline ice films (at 135 K), when the PT is mediated by hydroxyl ions (reported by Moon et al [69,70] and Kim et al [71] from reactive ion scattering) and for PT in pure water (Luz and Meiboom [72], obtained by proton magnetic relaxation measurements). The values of the energy barriers reported in the present work (around 2.3 kcal/mol ∼ 10 kJ/mol for the unconstrained system at 300 K, see above) agree well with the order of magnitude of the experimental measurements and with those obtained by Lockwood and Garofalini [42] and from previous estimation of the PT activation energy [43] although they cannot be properly considered as equivalent to activation energies of PT.…”

Section: Potentials Of Mean Force For Proton Transfermentioning

confidence: 99%

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Potentials of mean force in acidic proton transfer reactions in constrained geometries

Rabassa

2016

Molecular Simulation

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Free energy barriers associated to the transfer of an excess proton in water and related to the potentials of mean force in proton transfer episodes have been computed in a wide range of thermodynamic states, from low density amorphous ices to high temperature liquids under the critical point for unconstrained and constrained systems. The latter were represented by setups placed inside hydrophobic graphene slabs at the nanometric scale allocating a few water layers, namely one or two in the narrowest case. Waterproton and carbon-proton forces were modelled with a Multi-State Empirical Valence Bond method. As a general trend, a competition between the effects of confinement and temperature is observed on the local hydrogen-bonded structures around the lone proton and, consequently, on the mean force exerted by its environment on the water molecule carrying the proton. Free energy barriers estimated from the computed potentials of mean force tend to rise with the combined effect of increasing temperatures and the packing effect due to a larger extent of hydrophobic confinement. The main reason observed for such enhancement of the free energy barriers was the breaking of the second coordination shell around the lone proton.

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Section: Discussionsupporting

confidence: 74%

Section: Potentials Of Mean Force For Proton Transfermentioning

confidence: 99%

Potentials of mean force in acidic proton transfer reactions in constrained geometries

Rabassa

2016

Molecular Simulation

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“…Clear differences in mobility between the outermost and the inner water layers were established in the work by Nada and Furukawa (1997) and are, in fact, a ubiquitous feature of ice surfaces over a large range of temperatures (Bolton and Pettersson, 2000;Toubin et al, 2001;Grecea et al, 2004;Park et al, 2010). Consequently, techniques sensitive to the outermost surface layers will always get a higher water mobility than methods looking at the bulk of the disordered interface or at grain boundaries; the differences may well span orders of magnitude.…”

Section: Diffusion Of Water At the Ice Surfacementioning

confidence: 99%

A review of air–ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow

et al. 2014

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Abstract. Snow in the environment acts as a host to rich chemistry and provides a matrix for physical exchange of contaminants within the ecosystem. The goal of this review is to summarise the current state of knowledge of physical processes and chemical reactivity in surface snow with relevance to polar regions. It focuses on a description of impurities in distinct compartments present in surface snow, such as snow crystals, grain boundaries, crystal surfaces, and liquid parts. It emphasises the microscopic description of the ice surface and its link with the environment. Distinct differences between the disordered air–ice interface, often termed quasi-liquid layer, and a liquid phase are highlighted. The reactivity in these different compartments of surface snow is discussed using many experimental studies, simulations, and selected snow models from the molecular to the macro-scale. Although new experimental techniques have extended our knowledge of the surface properties of ice and their impact on some single reactions and processes, others occurring on, at or within snow grains remain unquantified. The presence of liquid or liquid-like compartments either due to the formation of brine or disorder at surfaces of snow crystals below the freezing point may strongly modify reaction rates. Therefore, future experiments should include a detailed characterisation of the surface properties of the ice matrices. A further point that remains largely unresolved is the distribution of impurities between the different domains of the condensed phase inside the snowpack, i.e. in the bulk solid, in liquid at the surface or trapped in confined pockets within or between grains, or at the surface. While surface-sensitive laboratory techniques may in the future help to resolve this point for equilibrium conditions, additional uncertainty for the environmental snowpack may be caused by the highly dynamic nature of the snowpack due to the fast metamorphism occurring under certain environmental conditions. Due to these gaps in knowledge the first snow chemistry models have attempted to reproduce certain processes like the long-term incorporation of volatile compounds in snow and firn or the release of reactive species from the snowpack. Although so far none of the models offers a coupled approach of physical and chemical processes or a detailed representation of the different compartments, they have successfully been used to reproduce some field experiments. A fully coupled snow chemistry and physics model remains to be developed.

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“…45,46 These subjects have been reviewed recently. 27,47 Ice surfaces offer a unique reaction environment, which is quite different from a liquid water or gas environment. Until recently, the study of reactions on ice surfaces at low temperatures has been very limited compared to that of aqueous or gas phase reactions.…”

Section: Reactive Ion Scattering Of Lowmentioning

confidence: 99%

“…Combined together, TP-RIS, TP-LES, and TPD observations indicate that the adsorption of SO 2 on ice produces three surfaces species: a solvated SO 2 species with a partial negative charge, a HSO 2 species, and an anionic HSO3-like species. 47 Because these species are efficiently formed even at the low temperatures, the hydrolysis of SO 2 must occur with very small or negligible energy barriers. Also, these species may correspond to distinct intermediate stages in the hydrolysis mechanism, because they are trapped on the ice surface via kinetic isolation at the low temperatures.…”

Section: Reactive Ion Scattering Of Lowmentioning

confidence: 99%

Reactive Ion Scattering of Low Energy Cs⁺from Surfaces. A Technique for Surface Molecular Analysis

Kang¹

2011

Bulletin of the Korean Chemical Society

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Although the currently available surface spectroscopic techniques provide powerful means of studying atoms and simple molecules on surfaces, the identification of complex molecules and functional groups is a major concern in surface analysis. This article describes a recently developed method of surface molecular analysis based on reactive ion scattering (RIS) of low energy (< 100 eV) Cs + beams. The RIS method can detect surface molecules via a mechanism in which a Cs + projectile picks up an adsorbate from the surface during the scattering process. The basic principles of the method are reviewed and its applications are discussed by showing several examples from studies of molecules and their reactions on surfaces.

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Some fundamental properties and reactions of ice surfaces at low temperatures

Cited by 61 publications

References 105 publications

Potentials of mean force in acidic proton transfer reactions in constrained geometries

Potentials of mean force in acidic proton transfer reactions in constrained geometries

A review of air–ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow

Reactive Ion Scattering of Low Energy Cs⁺from Surfaces. A Technique for Surface Molecular Analysis

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Some fundamental properties and reactions of ice surfaces at low temperatures

Cited by 61 publications

References 105 publications

Potentials of mean force in acidic proton transfer reactions in constrained geometries

Potentials of mean force in acidic proton transfer reactions in constrained geometries

A review of air–ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow

Reactive Ion Scattering of Low Energy Cs+from Surfaces. A Technique for Surface Molecular Analysis

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Reactive Ion Scattering of Low Energy Cs⁺from Surfaces. A Technique for Surface Molecular Analysis