Large variation of vacancy formation energies in the surface of crystalline ice

Watkins, Matthew; Pan, Ding; Wang, E. G.; Michaelides, Angelos; VandeVondele, Joost; Slater, Ben

doi:10.1038/nmat3096

Cited by 69 publications

(99 citation statements)

References 36 publications

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“…2). According to a previous study by Watkins, et al (10), when a molecule is removed from ice surface, which is related to the premelting of ice, the vacancy formation energy varies greatly, partially due to the local electric field created by the dangling protons. How about adsorption energy in the opposite physical/ chemical process-the adsorption process which is related to the initial growth of ice?…”

Section: Resultsmentioning

confidence: 99%

“…It has long been recognized that the adsorption properties depend on the structure of the ice surface (6)(7)(8)(9). However, it is still striking to see that many properties of ice surfaces vary greatly even on a prefect ice surface where the oxygen atoms are ordered in a hexagonal lattice (10)(11)(12)(13)). Yet, due to the complexity of the surface structure at the atomic level, our understandings of the activity and adsorption property on the ice surface are still far from consistent and complete.…”

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confidence: 99%

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Role of proton ordering in adsorption preference of polar molecule on ice surface

Sun

Pan

et al. 2012

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

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Adsorption of polar monomers on ice surface, relevant to the physical/chemical reaction in ice clouds as well as growth of ice, remains an open issue partially due to the unusual surface characteristics with protons at the top layer of ice. Using first-principle calculations, we explore the adsorption properties of ice surface in terms of a surface proton order parameter, which characterizes the inhomogeneity of the dangling atoms on ice surface. We show that, due to an effective electric field created by dangling OH bonds and lone pairs of water molecules not only directly neighboring but also further away from the adsorbed polar molecule on the ice surface, the adsorption energy of polar monomer on ice surface exhibits large variance and a strong correlation with the proton order parameter of ice surface. Our results about the positive correlation between the inhomogeneity of ice surface and adsorption energies suggest that the physical/chemical reactions as well as the growth of ice may prefer to occur firstly on surfaces with larger proton order parameter.surface science | ice basal surface | ice growth | ice basal plane I ce, one of the most abundant materials on earth, plays an important role in interstellar phenomena, life in the cryosphere and global climate (1-3). Adsorption on ice surface, especially hexagonal ice, is related to the fundamental question of how ice particles grow into hexagonal ice crystal or snow flakes, and what kind of roles it plays for the reactive and catalytic properties of atmospheric ice associated with environment-related issues (1-4). For instance, the ice surface acts as a catalyst in heterogeneous physical/chemical reactions leading to the destruction of ozone (5). It has long been recognized that the adsorption properties depend on the structure of the ice surface (6-9). However, it is still striking to see that many properties of ice surfaces vary greatly even on a prefect ice surface where the oxygen atoms are ordered in a hexagonal lattice (10-13). Yet, due to the complexity of the surface structure at the atomic level, our understandings of the activity and adsorption property on the ice surface are still far from consistent and complete.At interfaces, the Bernal-Fowler-Pauling ice rule (14, 15) cannot be obeyed; that is, nearest neighboring water molecules cannot satisfy all hydrogen bonds, thus forming dangling protons and lone pairs. Recent works (16-18) have shown that the inhomogeneity of dangling atoms, which can be characterized by a proton order parameter (17), is important for the energies of water ice surfaces (17,18). This order parameter, C OH , characterizing the arrangement of dangling OH bonds on the ice surface (17), is defined aswhere N OH is the total number of dangling OH bonds on the surface and c i is the number of the nearest neighboring dangling OH bonds around the ith OH bond. For the ice slab without dipole moment perpendicular to the surface, the order parameter ranges from 2 to 6 (17). We note that the most ordered dangling OH distribution on...

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Role of proton ordering in adsorption preference of polar molecule on ice surface

Sun

Pan

et al. 2012

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

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“…2 ) and with the improvements expected for a hybrid functional. 58 Ultimately, this is a result of the underestimation of the band gap by semi-local functionals, a deficiency that is, also in water ice, significantly improved by hybrid functionals.…”

Section: Methodsmentioning

confidence: 96%

Dielectric Properties of Water Ice, the Ice Ih/XI Phase Transition, and an Assessment of Density Functional Theory

et al. 2014

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The dielectric properties of the hydrogen disordered hexagonal phase (Ih) of water ice have been computed using density functional theory (DFT) based Monte Carlo simulations in the isobaric isothermal ensemble. Temperature dependent data yield a fit for the Curie-Weiss law of the system and hence a prediction of the temperature of the phase transition from the Ih phase to the hydrogen ordered ice XI phase. Direct simulations around the phase transition temperature confirm and refine the predicted phase transition temperatures and provide data for further properties, such as the linear thermal expansion coefficient. Results have been obtained with both hybrid and semilocal density functionals, which yields insight in the performance of the electronic structure method. In particular, the hybrid functional yields significantly more realistic dielectric constants than the semilocal variant, namely epsilon approximate to 116 as opposed to epsilon approximate to 151 at 273 K (epsilon(experiment) = 95). This can be attributed to the tendency of semilocal functionals to be biased to configurations with a large dipole moment, and their overestimation of the dipole moments of these configurations. This is also reflected in the estimates of the Ih/XI transition temperature, which is 70-80 and 90-100 K for the hybrid and semilocal functional respectively. DFT based sampling of the millions of configurations necessary for this work has been enabled by a Tree Monte Carlo algorithm, designed for massively parallel computers. with both hybrid and semi-local density functionals, which yields insight in the performance of the electronic structure method. In particular, the hybrid functional yields significantly more realistic dielectric constants than the semi-local variant, namely ε ≈ 116 as opposed to ε ≈ 151 at 273K (ε experiment = 95). This can be attributed to the tendency of semi-local functionals to be biased to configurations with a large dipole moment, and their overestimation of the dipole moments of these configurations. This is also reflected in the estimates of the Ih/XI transition temperature, which is 70-80K and 90-100K for the hybrid and semi-local functional respectively.DFT based sampling of the millions of configurations necessary for this work has been enabled by a Tree Monte Carlo algorithm, designed for massively parallel computers.

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“…However, the underlying mechanism of surface melting is still a matter of debate and is far from completely understood, despite numerous experiments and theories, including numerical simulations, that indicate its existence [8][9][10][11][12][13][14]. The major bottleneck is the experimental difficulties in the way of direct and accurate observation of QLLs, whose thicknesses are assumed to be less than tens of nanometer, under well-controlled conditions of temperature and vapor pressure.…”

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confidence: 99%

In situDetermination of Surface Tension-to-Shear Viscosity Ratio for Quasiliquid Layers on Ice Crystal Surfaces

et al. 2015

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We have experimentally determined the surface tension-to-shear viscosity ratio (the so-called characteristic velocity) of quasiliquid layers (QLLs) on ice crystal surfaces from their wetting dynamics. Using an advanced optical microscope, whose resolution reaches the molecular level in the height direction, we directly observed the coalescent process of QLLs and followed the relaxation modes of their contact lines. The relaxation dynamics is known to be governed by the characteristic velocity, which allows us to access the physical properties of QLLs in a noninvasive way. Here we quantitatively demonstrate that QLLs, when completely wetting ices, have a thickness of 9 AE 3 nm and an approximately 200 times lower characteristic velocity than bulk water, whereas QLLs, when partially wetting ices, have a velocity that is 20 times lower than the bulk. This indicates that ice crystal surfaces significantly affect the physical properties of QLLs localized near the surfaces at a nanometer scale.

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Large variation of vacancy formation energies in the surface of crystalline ice

Cited by 69 publications

References 36 publications

Role of proton ordering in adsorption preference of polar molecule on ice surface

Role of proton ordering in adsorption preference of polar molecule on ice surface

Dielectric Properties of Water Ice, the Ice Ih/XI Phase Transition, and an Assessment of Density Functional Theory

In situDetermination of Surface Tension-to-Shear Viscosity Ratio for Quasiliquid Layers on Ice Crystal Surfaces

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