Growth of multilayer ice films and the formation of cubic ice imaged with STM

Thürmer, Konrad; Bartelt, N. C.

doi:10.1103/physrevb.77.195425

Cited by 84 publications

(105 citation statements)

References 36 publications

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“…As reported by Kimmel et al (36) and confirmed by our previous STM work (31), water deposited at 135-150 K onto Pt(111) first forms a one-molecule-thin wetting layer (37)(38)(39)(40). Then, isolated 3D ice crystallites emerge and eventually, at thicknesses of ∼3-10 nm, coalesce into a continuous multilayer film.…”

Section: Resultssupporting

confidence: 57%

“…We now discuss the growth situation that arises after the 3D crystallites have coalesced into a continuous film. Previously we had shown that the coalescence of these crystallites across substrate steps generates screw dislocations, which produce surface steps that allow spiral growth without nucleation (31). At film thicknesses accessible with STM, i.e., <10 nm, these spirals mostly lead to cubic ice.…”

Section: Resultsmentioning

confidence: 99%

“…The subsequent growth proceeds by expanding this green top layer, thereby producing ice of uniform intralayer stacking, i.e., cubic ice. Our previous STM experiments (31) Schematic of the experiment to test whether growth via nucleation leads to cubic or hexagonal ice. The two orientations of the triangular 2D islands reflect the two possible ways of intralayer stacking (blue or green).…”

Section: Resultsmentioning

confidence: 99%

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Formation of hexagonal and cubic ice during low-temperature growth

Thürmer

Nie

2013

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

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106

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From our daily life we are familiar with hexagonal ice, but at very low temperature ice can exist in a different structure--that of cubic ice. Seeking to unravel the enigmatic relationship between these two low-pressure phases, we examined their formation on a Pt (111) substrate at low temperatures with scanning tunneling microscopy and atomic force microscopy. After completion of the onemolecule-thick wetting layer, 3D clusters of hexagonal ice grow via layer nucleation. The coalescence of these clusters creates a rich scenario of domain-boundary and screw-dislocation formation. We discovered that during subsequent growth, domain boundaries are replaced by growth spirals around screw dislocations, and that the nature of these spirals determines whether ice adopts the cubic or the hexagonal structure. Initially, most of these spirals are single, i.e., they host a screw dislocation with a Burgers vector connecting neighboring molecular planes, and produce cubic ice. Films thicker than ∼20 nm, however, are dominated by double spirals. Their abundance is surprising because they require a Burgers vector spanning two molecular-layer spacings, distorting the crystal lattice to a larger extent. We propose that these double spirals grow at the expense of the initially more common single spirals for an energetic reason: they produce hexagonal ice.ice growth mechanisms | molecular surface steps | molecular-layer nucleation | scanning probe microscopy | spiral growth O wing to its ubiquity in nature, ice and its structural properties have inspired widespread interest (1, 2). Not long after the introduction of X-ray diffraction in 1912, the structure of the most common modification of ice, hexagonal ice Ih, had already been investigated extensively (1-6). In 1942, König (7) discovered that at low temperatures water occasionally crystallizes into a different modification, cubic ice Ic. Subsequently, cubic ice has been produced in the laboratory, e.g., by condensing water vapor onto cooled substrates (7-11), by heating amorphous solid water (7-9), by supercooling liquid water droplets (12-14) or clusters (15), or by freezing high-pressure phases of ice and reheating them at atmospheric pressure (16)(17)(18)(19). Cubic ice has been proposed to also occur naturally, e.g., in the earth's atmosphere (13,(20)(21)(22)(23)(24) and in comets (25,26). However, even after thousands of articles dedicated to ice formation have appeared, important questions regarding fundamental growth mechanisms of ice remain. Some of these questions concerning the competition between the two lowpressure crystalline phases ice Ih and ice Ic are addressed in this paper.Ice Ih and ice Ic have been observed to coexist at temperatures up to 240 K (10-12, 18, 27, 28). When ice Ic is heated above 170 K it transforms irreversibly into ice Ih. The release of a measurable amount of heat (on the order of 35 J/mol) (17-19) establishes hexagonal ice as the equilibrium structure above 170 K. Below 170 K no phase transformation has been observed, allowing for the poss...

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Section: Resultssupporting

confidence: 57%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Formation of hexagonal and cubic ice during low-temperature growth

Thürmer

Nie

2013

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

Self Cite

106

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“…5. For ice on Pt (111), both the surface steps and screw dislocations are critical in the formation of metastable cubic structure (and not the hexagonal one) and in the growth (24).…”

Section: Resultsmentioning

confidence: 99%

Ordered water structure at hydrophobic graphite interfaces observed by 4D, ultrafast electron crystallography

Yang

Zewail

2009

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

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Interfacial water has unique properties in various functions. Here, using 4-dimensional (4D), ultrafast electron crystallography with atomic-scale spatial and temporal resolution, we report study of structure and dynamics of interfacial water assembly on a hydrophobic surface. Structurally, vertically stacked bilayers on highly oriented pyrolytic graphite surface were determined to be ordered, contrary to the expectation that the strong hydrogen bonding of water on hydrophobic surfaces would dominate with suppressed interfacial order. Because of its terrace morphology, graphite plays the role of a template. The dynamics is also surprising. After the excitation of graphite by an ultrafast infrared pulse, the interfacial ice structure undergoes nonequilibrium ''phase transformation'' identified in the hydrogen-bond network through the observation of structural isosbestic point. We provide the time scales involved, the nature of ice-graphite structural dynamics, and relevance to properties related to confined water.hydrophilic and hydrophobic interactions ͉ ice-substrate structure and dynamics ͉ nonequilibrium phase transition W ater at interfaces is fundamental to the understanding of various phenomena, such as wetting, molecular recognition and macromolecular folding. When compared with bulk phases (1, 2), the nano-scale interface is believed to have a unique function in nanotribology (3, 4), chemical reactivity (4-6) and biological structure and dynamics (7-10). From the structural point of view, considering the energetics, the determining factor at interfaces is the delicate balance of hydrogen bonding among water molecules and the comparable interactions with a substance, defining the 2 extremes of hydrophobic and hydrophilic behavior. However, the time scales of structural dynamics are important for defining the microscopic mechanisms of relaxations and the role of substrate structure and morphology (11). For water ice on a hydrophilic substrate, the ordered layers are evidenced by their diffraction (Bragg spots), and this long-range order is lost when the ice assembly becomes at a distance from the substrate (12). On hydrophobic surfaces, the expected picture is that randomly oriented crystallites form with no interfacial long-range order, because of the stronger intermolecular interactions when compared with those of water-substrate.In the current study, we report the determination of structure and dynamical behavior of water assembly on highly oriented pyrolytic graphite (HOPG), a hydrophobic substrate. Using ultrafast electron crystallography (UEC) (11) that has been described in detail in refs. 12 and 13, provides, through diffraction, the position of atomic planes and the temporal change of the structure. Electron crystallography (14), because of the large electron scattering cross section, is ideal for these surface and interface probings. Here, it is shown that the layered structure of HOPG serves as a substrate and promotes the crystalline order in the ice thin film along the surface normal direction...

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“…STM measurements were performed at T < 115 K. To avoid tip-induced damage, we kept the tunneling current <1 pA. Tip voltage was between 0.2 and 1 V. We determined the crystallographic directions of the Pt (111) substrate by evaluating the registry of atomic positions on both sides of an atomic Pt step [32,144]. All STM images presented herein are oriented in the same way relative to the substrate.…”

Section: Methodsmentioning

confidence: 99%

Studies of the viscoelastic properties of water confined between surfaces of specified chemical nature.

Houston¹,

Grest²,

Moore³

et al. 2010

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This report summarizes the work completed under the Laboratory Directed Research and Development (LDRD) project 10-0973 of the same title. Understanding the molecular origin of the no-slip boundary condition remains vitally important for understanding molecular transport in biological, environmental and energy-related processes, with broad technological implications. Moreover, the viscoelastic properties of fluids in nanoconfinement or near surfaces are not well-understood. We have critically reviewed progress in this area, evaluated key experimental and theoretical methods, and made unique and important discoveries addressing these and related scientific questions. Thematically, the discoveries include insight into the orientation of water molecules on metal surfaces, the premelting of ice, the nucleation of water and alcohol vapors between surface asperities and the lubricity of these molecules when confined inside nanopores, the influence of water nucleation on adhesion to salts and silicates, and the growth and superplasticity of NaCl nanowires.

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Growth of multilayer ice films and the formation of cubic ice imaged with STM

Cited by 84 publications

References 36 publications

Formation of hexagonal and cubic ice during low-temperature growth

Formation of hexagonal and cubic ice during low-temperature growth

Ordered water structure at hydrophobic graphite interfaces observed by 4D, ultrafast electron crystallography

Studies of the viscoelastic properties of water confined between surfaces of specified chemical nature.

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