The single-crystal, basal face of ice Ih investigated with sum frequency generation

Groenzin, Henning; Li, Irene; Buch, V.; Shultz, Mary Jane

doi:10.1063/1.2801642

Cited by 55 publications

(78 citation statements)

References 65 publications

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“…Fig. 5 shows a comparison of the computed spectrum with the experimental ppp polarization H-bonded OH-stretch spectrum measured in the Shultz laboratory (34,35). The lowfrequency peak a was assigned in ref.…”

Section: Resultsmentioning

confidence: 99%

Proton order in the ice crystal surface

Buch

Groenzin

et al. 2008

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

131

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The physics of the ice crystal surface and its interaction with adsorbates are not only of fundamental interest but also of considerable importance to terrestrial and planetary chemistry. Yet the atomic-level structure of even the pristine ice surface at low temperature is still far from well understood. This computational study focuses on the pattern of dangling H and dangling O (lone pairs) atoms at the basal ice surface. Dangling atoms serve as binding sites for adsorbates capable of hydrogen-and electrostatic bonding. Extension of the well known orientational disorder (''proton disorder'') of bulk crystal ice to the surface would naturally suggest a disordered dangling atom pattern; however, extensive computer simulations employing two different empirical potentials indicate significant free energy preference for a striped phase with alternating rows of dangling H and dangling O atoms, as suggested long ago by Fletcher [Fletcher NH (1992) Philos Mag 66:109 -115]. The presence of striped phase domains within the basal surface is consistent with the hitherto unexplained minor fractional peaks in the helium diffraction pattern observed 10 years ago. Compared with the disordered model, the striped model yields improved agreement between computations and experimental ppp-polarized sum frequency generation spectra.ice surface ͉ Monte Carlo simulations ͉ surface order ͉ dangling atoms ͉ ice-adsorbate interaction W ater ice is an intellectually challenging and fundamentally important solid. Ice and ice particles play a basic role in terrestrial, atmospheric, planetary, and interstellar phenomena (1-3). The remarkable properties of ice are determined by the unique ability of H 2 O to form four relatively strong hydrogen bonds to four neighboring water molecules, in an approximately tetrahedral arrangement. This gives rise to a rich bulk phase diagram comprising a variety of crystalline phases, in addition to muchdebated amorphous phases (1).Under ambient conditions, hexagonal ice is the dominant solid form of H 2 O. Here we focus on the surface structure of hexagonal ice, which hosts a variety of chemical reactions in natural environments; perhaps the most famous example being the sequence of reactions leading to ozone-hole formation, which is initiated by HCl and ClO adsorption on frozen stratospheric cloud particles (4). The interaction of ice with molecules, ions, and electrons is affected by the solvating properties of its surface. It has long been recognized that these properties are directly related to the structure and dynamics of the surface H-bond network, which has consequently received considerable attention in past research (see, for example, refs. 1, 3, and 5-16).Here, we address a feature of the ice surface that has not received extensive attention but that is expected to significantly influence its properties, including its interaction with adsorbates. Specifically, we argue that the pattern of dangling H (d-H) and dangling O (d-O) atoms on the ice surface is composed of ordered striped domains, with a...

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Section: Resultsmentioning

confidence: 99%

Proton order in the ice crystal surface

Buch

Groenzin

et al. 2008

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

131

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“…158,161,163,[172][173][174][175][176][177] Experimental studies using surface sensitive methods at liquid water and ice surfaces provide important complementary information. 176,[178][179][180] However, modeling heterogeneous reactions in these complex environments remains a challenge. The ionization of acids and proton recombination are important processes in environmental waters at water and ice surfaces.…”

Section: Cluster Models For Condensed Phases Aerosols and Interfacesmentioning

confidence: 99%

Perspective: Water cluster mediated atmospheric chemistry

Vaida

2011

The Journal of Chemical Physics

279

249

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The importance of water in atmospheric and environmental chemistry initiated recent studies with results documenting catalysis, suppression and anti-catalysis of thermal and photochemical reactions due to hydrogen bonding of reagents with water. Water, even one water molecule in binary complexes, has been shown by quantum chemistry to stabilize the transition state and lower its energy. However, new results underscore the need to evaluate the relative competing rates between reaction and dissipation to elucidate the role of water in chemistry. Water clusters have been used successfully as models for reactions in gas-phase, in aqueous condensed phases and at aqueous surfaces. Opportunities for experimental and theoretical chemical physics to make fundamental new discoveries abound. Work in this field is timely given the importance of water in atmospheric and environmental chemistry.

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“…Whenever the thickness of a liquid layer is sufficiently large, either because the system undergoes a surface melting or an incomplete surface melting (with a significantly thick liquid layer), it is not possible to superheat a solid. Due to the ubiquitous character of water, it is of particular interest to determine the structure of the surface of ice 14,15,16,17 and, in particular, the structure of a water liquid layer on ice at the temperatures below the melting point. The solution to that problem is not only important from a fundamental point of view, but also from a practical point of view.…”

Section: Introductionmentioning

confidence: 99%

The thickness of a liquid layer on the free surface of ice as obtained from computer simulation

Conde¹,

Vega²,

Patrykiejew³

2008

The Journal of Chemical Physics

166

216

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Molecular dynamic simulations were performed for ice I h with a free surface by using four water models, SPC/E, TIP4P, TIP4P/Ice and TIP4P/2005. The behavior of the basal plane, the primary prismatic plane and of the secondary prismatic plane when exposed to vacuum was analyzed. We observe the formation of a thin liquid layer at the ice surface at temperatures below the melting point for all models and the three planes considered. For a given plane it was found that the thickness of a liquid layer was similar for different water models, when the comparison is made at the same undercooling with respect to the melting point of the model. The liquid layer thickness is found to increase with temperature. For a fixed temperature it was found that the thickness of the liquid layer decreases in the following order: the basal plane, the primary prismatic plane, and the secondary prismatic plane. For the TIP4P/Ice model, a model reproducing the experimental value of the melting temperature of ice, the first clear indication of the formation of a liquid layer appears at about -100 Celsius for the basal plane, at about -80 Celsius for the primary prismatic plane and at about -70 Celsius for the secondary prismatic plane.

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The single-crystal, basal face of ice Ih investigated with sum frequency generation

Cited by 55 publications

References 65 publications

Proton order in the ice crystal surface

Proton order in the ice crystal surface

Perspective: Water cluster mediated atmospheric chemistry

The thickness of a liquid layer on the free surface of ice as obtained from computer simulation

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