Atomic force microscopy observation of surface morphologies and measurements of local contact potential differences of amorphous solid water samples deposited at 15 and 100 K.

We use an ultra-high vacuum cryogenic atomic force microscope to investigate the surface morphology of amorphous solid water (ASW) prepared by oblique deposition of water vapor onto Si(111)7 × 7 substrates at temperatures of 15 and 100 K. Height-height correlation function analysis of topographic images suggests that ASW at 15 K has a columnar structure and that the typical diameter of the column is 5-10 nm. At 100 K, the typical diameter is 10-30 nm, although columnar features are less prominent. The surface roughness (i.e., deviation of the height) is greater at 15 K than at 100 K, indicating that the surface at 100 K exhibits a relatively flat morphology. This result implies that transient diffusion of deposited water molecules affects the surface morphology at 100 K. In addition, measurements of the local contact potential difference between the tip and the ASW surface suggest that the magnitude of the negative surface potential at the microscopic scale, which is attributed to spontaneous polarisation, cannot simply be scaled by the thickness of ASW as predicted in previous experiments with Kelvin probes.

Chiral Spinodal-like Ordering of Homoimmiscible Water at Interface between Water and Chiral Ice III.

Diversity in structures of water endowed by a hydrogen-bonding network plays crucial roles in wide varieties of phenomena in nature. Chiral ordering of water molecules is an intriguing phenomenon from the viewpoint of bimolecular functions. However, experimental reports on chiral ordering have been limited to the water molecules interacting with biomolecules on the molecular scale. It remains unclear whether pure liquid water forms long-range chiral ordering without any interaction with biomolecules. Here, we show that chiral anisotropy can be observed in the macro/mesoscopic network pattern of an unknown water layer formed via spinodal phase separation-like dynamics at the interface between water and ice III with a chiral crystal structure. We named this unknown water homoimmiscible water. Our observations infer that the unknown water is a chiral liquid crystal. This possibility opens new avenues for a wide variety of research fields such as liquid polymorphism, biology, earth and planetary science, and so forth from the perspective of chirality.

Anisotropy in spinodal-like dynamics of unknown water at ice V-water interface.

Experimentally demonstrating the existence of waters with local structures unlike that of common water is critical for understanding both the origin of the mysterious properties of water and liquid polymorphism in single component liquids. At the interfaces between water and ices Ih, III, and VI grown/melted under pressure, we previously discovered low- and high-density unknown waters, that are immiscible with the surrounding water. Here, we show, by in-situ optical microscopy, that an unknown water appears at the ice V-water interface via spinodal-like dynamics. The dewetting dynamics of the unknown water indicate that its characteristic velocity is ~ 90 m/s. The time evolution of the characteristic length of the spinodal-like undulation suggests that the dynamics may be described by a common model for spinodal decomposition of an immiscible liquid mixture. Spinodal-like dewetting dynamics of the unknown water transiently showed anisotropy, implying the property of a liquid crystal.

UV-Induced Formation of Ice XI Observed Using an Ultra-High Vacuum Cryogenic Transmission Electron Microscope and its Implications for Planetary Science.

The occurrence of hydrogen atom-ordered form of ice Ih, ice XI, in the outer Solar System has been discussed based on laboratory experiments because its ferroelectricity influences the physical processes in the outer Solar System. However, the formation of ice XI in that region is still unknown due to a lack of formation conditions at temperatures higher than 72 K and the effect of UV-rays on the phase transition from ice I to ice XI. As a result, we observed the UV-irradiation process on ice Ih and ice Ic using a newly developed ultra-high vacuum cryogenic transmission electron microscope. We found that ice Ih transformed to ice XI at temperatures between 75 and 140 K with a relatively small UV dose. Although ice Ic partially transformed to ice XI at 83 K, the rate of transformation was slower than for ice Ih. These findings point to the formation of ice XI at temperatures greater than 72 K via UV irradiation of ice I crystals in the Solar System; icy grains and the surfaces of icy satellites in the Jovian and Saturnian regions.

Delivery of Electrons by Proton-Hole Transfer in Ice at 10 K: Role of Surface OH Radicals.

Although water ice has been widely accepted to carry a positive charge via the transfer of excess protons through a hydrogen-bonded system, ice was recently found to be a negative charge conductor upon simultaneous exposure to electrons and ultraviolet photons at temperatures below 50 K. In this work, the mechanism of electron delivery was confirmed experimentally by both measuring currents through ice and monitoring photodissociated OH radicals on ice by using a novel method. The surface OH radicals significantly decrease upon the appearance of negative current flow, indicating that the electrons are delivered by proton-hole (OH-) transfer in ice triggered by OH- production on the surface. The mechanism of proton-hole transfer was rationalized by density functional theory calculations.

CH3O Radical Binding on Hexagonal Water Ice and Amorphous Solid Water.

Binding energies of the CH3O radical on hexagonal water ice (Ih) and amorphous solid water (ASW) were calculated using the ONIOM(QM:MM) method. A range of binding energies is found (0.10-0.50 eV), and the average binding energy is 0.32 eV. The CH3O radical binding on the ASW surfaces is stronger than on the Ih surfaces. The computed binding energies from the ONIOM(wB97X-D/def2-TZVP:AMBER) and wB97X-D/def2-TZVP methods agree quite well. Therefore, the ONIOM(QM:MM) method is expected to give accurate binding energies at a low computational cost. Binding energies from the ONIOM(wB97X-D/def2-TZVP:AMBER) and ONIOM(wB97X-D/def2-TZVP:AMOEBA09) methods differ noticeably, indicating that the choice of force field matters. According to the energy decomposition analysis, the electrostatic interactions and Pauli repulsions between the CH3O radical and ice play a crucial role in the binding energy. This study gives quantitative insights into the CH3O radical binding on interstellar ices.

Quantitative Anisotropic Analysis of Molecular Orientation in Amorphous N2O at 6 K by Infrared Multiple-Angle Incidence Resolution Spectrometry.

The existence of molecular orientational order in nanometer-thick films of molecules has long been implied by surface potential measurements. However, direct quantitative determination of the molecular orientation is challenging, especially for metastable amorphous thin films at low temperatures. This study quantifies molecular orientation in amorphous N2O at 6 K using infrared multiple-angle incidence resolution spectrometry (IR-MAIRS). The intensity ratio of the weak antisymmetric stretching vibration band of the 14N15NO isotopomer between the in-plane and out-of-plane IR-MAIRS spectra provides an average molecular orientation angle of 65° from the surface normal. No discernible change is observed in the orientation angle when a different substrate material is used (Si and Ar) at 6 K or the Si substrate temperature is changed in the range of 6-14 K. This suggests that the transient mobility of N2O during physisorption is key in governing the molecular orientation in amorphous N2O.

In vivo characterization of the structures of films of a fatty acid and an alcohol adsorbed on the skin surface.

An in vivo analysis of stearyl alcohol and stearic acid films on the skin surface using polarized infrared-external reflection spectroscopy revealed that whether the sample molecules adopt an energetically stable conformation and orientation strongly depends on the molecular functionalities and sample preparation conditions. For stearic acid, even the difference in solute concentration between 0.1 and 0.5 wt% results in a different molecular conformation and orientation. This illustrates that the molecular organization of the adsorbate on the skin surface is sensitively determined by the kinetics of the sample film growth, not by the simple thermodynamic equilibrium with the skin temperature.

High-Density Liquid Water at a Water-Ice Interface.

Because ice surfaces catalyze various key chemical reactions impacting nature and human life, the structure and dynamics of interfacial layers between water vapor and ice have been extensively debated with attention to the quasi-liquid layer. Other interfaces between liquid water and ice remain relatively underexplored, despite their importance and abundance on the Earth and icy extraterrestrial bodies. By in situ optical microscopy, we found that a high-density liquid layer, distinguishable from bulk water, formed at the interface between water and high-pressure ice III or VI, when they were grown or melted in a sapphire anvil cell. The liquid layer showed a bicontinuous pattern, indicating that immiscible waters with distinct structures were separated on the interfaces in a similar manner to liquid-liquid phase separation through spinodal decomposition. Our observations not only provide a novel opportunity to explore ice surfaces but also give insight into the two kinds of structured water.

Precometary organic matter: A hidden reservoir of water inside the snow line.

The origin and evolution of solar system bodies, including water on the Earth, have been discussed based on the assumption that the relevant ingredients were simply silicates and ices. However, large amounts of organic matter have been found in cometary and interplanetary dust, which are recognized as remnants of interstellar/precometary grains. Precometary organic matter may therefore be a potential source of water; however, to date, there have been no experimental investigations into this possibility. Here, we experimentally demonstrate that abundant water and oil are formed via the heating of a precometary-organic-matter analog under conditions appropriate for the parent bodies of meteorites inside the snow line. This implies that H2O ice is not required as the sole source of water on planetary bodies inside the snow line. Further, we can explain the change in the oxidation state of the Earth from an initially reduced state to a final oxidized state. Our study also suggests that petroleum was present in the asteroids and is present in icy satellites and dwarf planets.

Nucleobase synthesis in interstellar ices.

The synthesis of nucleobases in natural environments, especially in interstellar molecular clouds, is the focus of a long-standing debate regarding prebiotic chemical evolution. Here we report the simultaneous detection of all three pyrimidine (cytosine, uracil and thymine) and three purine nucleobases (adenine, xanthine and hypoxanthine) in interstellar ice analogues composed of simple molecules including H2O, CO, NH3 and CH3OH after exposure to ultraviolet photons followed by thermal processes, that is, in conditions that simulate the chemical processes accompanying star formation from molecular clouds. Photolysis of primitive gas molecules at 10 K might be one of the key steps in the production of nucleobases. The present results strongly suggest that the evolution from molecular clouds to stars and planets provides a suitable environment for nucleobase synthesis in space.

Probing the Molecular Structure and Orientation of the Leaf Surface of Brassica oleracea L. by Polarization Modulation-Infrared Reflection-Absorption Spectroscopy.

The surface of most aerial plant organs is covered with the cuticle, a membrane consisting of a variety of organic compounds, including waxes, cutin (a polyester) and polysaccharides. The cuticle serves as the multifunctional interface between the plant and the environment, and plays a major role in protecting plants against various environmental stress factors. Characterization of the molecular arrangements in the intact cuticle is critical for the fundamental understanding of its physicochemical properties; however, this analysis remains technically challenging. Here, we describe the nondestructive characterization of the intact cuticle of Brassica oleracea L. leaves using polarization modulation-infrared (IR) reflection-absorption spectroscopy (PM-IRRAS). PM-IRRAS has a probing depth of less than several hundreds of nanometers, and reveals the crystalline structure of the wax covering the cuticle surface (epicuticular wax) and the nonhydrogen-bonding character of cutin. Combined analysis using attenuated total reflection-IR spectra suggested that hemicelluloses xylan and xyloglucan are present in the outer cuticle region close to the epicuticular wax, whereas pectins are dominant in the inner cuticle region (depth of ≤2 µm). PM-IRRAS can also determine the average orientation of the cuticular molecules, as indicated by the positive and negative spectral peaks. This unique advantage reveals the orientational order in the intact cuticle; the hydrocarbon chains of the epicuticular wax and cutin and the backbones of hemicelluloses are oriented perpendicular to the leaf surface. PM-IRRAS is a versatile, informative and easy-to-use technique for studying plant cuticles because it is nondestructive and does not require sample pretreatment and background measurements.

In Situ Nondestructive Analysis of Kalanchoe pinnata Leaf Surface Structure by Polarization-Modulation Infrared Reflection-Absorption Spectroscopy.

The outermost surface of the leaves of land plants is covered with a lipid membrane called the cuticle that protects against various stress factors. Probing the molecular-level structure of the intact cuticle is highly desirable for understanding its multifunctional properties. We report the in situ characterization of the surface structure of Kalanchoe pinnata leaves using polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS). Without sample pretreatment, PM-IRRAS measures the IR spectra of the leaf cuticle of a potted K. pinnata plant. The peak position of the CH2-related modes shows that the cuticular waxes on the leaf surface are mainly crystalline, and the alkyl chains are highly packed in an all-trans zigzag conformation. The surface selection rule of PM-IRRAS revealed the average orientation of the cuticular molecules, as indicated by the positive and negative signals of the IR peaks. This unique property of PM-IRRAS revealed that the alkyl chains of the waxes and the main chains of polysaccharides are oriented almost perpendicular to the leaf surface. The nondestructive, background-free, and environmental gas-free nature of PM-IRRAS allows the structure and chemistry of the leaf cuticle to be studied directly in its native environment.

Liquid-like behavior of UV-irradiated interstellar ice analog at low temperatures.

Interstellar ice is believed to be a cradle of complex organic compounds, commonly found within icy comets and interstellar clouds, in association with ultraviolet (UV) irradiation and subsequent warming. We found that UV-irradiated amorphous ices composed of H2O, CH3OH, and NH3 and of pure H2O behave like liquids over the temperature ranges of 65 to 150 kelvin and 50 to 140 kelvin, respectively. This low-viscosity liquid-like ice may enhance the formation of organic compounds including prebiotic molecules and the accretion of icy dust to form icy planetesimals under certain interstellar conditions.

Fast crystalline ice formation at extremely low temperature through water/neon matrix sublimation.

Crystalline ice formation requires water molecules to be sufficiently mobile to find and settle on the thermodynamically most stable site. Upon cooling, however, diffusion and rearrangement become increasingly kinetically difficult. Water ice grown by the condensation of water vapor in laboratory is thus generally assumed to be in a metastable amorphous form below 100 K. Here, we demonstrate the possibility of crystalline ice formation at extremely low temperature using a water/neon matrix (1/1000, 30 000 monolayers) prepared at 6 K, which is subsequently warmed to 11-12 K. In situ infrared spectroscopy revealed the assembly of the dispersed water molecules, forming crystalline ice I during the sublimation of the neon matrix for 40-250 seconds. This finding indicates that the high mobility of the water molecules during matrix sublimation can overcome the kinetic barrier to form crystals even at extremely low temperature.

Simulations and spectra of water in CO matrices.

Models for the inclusion of water molecules in carbon monoxide matrices are developed using density functional theory applied to amorphous solid systems. The models cover a large range of systems for smaller or larger CO matrices with different water content, consisting of either individual H2O molecules or small clusters linked by H-bonds. The vibrational spectra of the samples are predicted at the minimum of their potential energy surface. The spectra allow instances where the water molecules remain isolated or form aggregates to be discerned, and they also provide an indication of the strength of the H-bonding, when present. The calculations support recent experimental observations that linked IR bands at 3707 cm-1 and 3617 cm-1 to the presence of unbound water molecules in water-poor CO/H2O mixed ices. Assignment of some observed bands to water dimers or trimers is suggested as well. The residual static pressure in fixed-volume simulation cells is also calculated.

Surface Temperature Dependence of Hydrogen Ortho-Para Conversion on Amorphous Solid Water.

The surface temperature dependence of the ortho-to-para conversion of H_{2} on amorphous solid water is first reported. A combination of photostimulated desorption and resonance-enhanced multiphoton ionization techniques allowed us to sensitively probe the conversion on the surface of amorphous solid water at temperatures of 9.2-16 K. Within a narrow temperature window of 8 K, the conversion time steeply varied from ∼4.1×10^{3} to ∼6.4×10^{2} s. The observed temperature dependence is discussed in the context of previously suggested models and the energy dissipation process. The two-phonon process most likely dominates the conversion rate at low temperatures.

Statistical ortho-to-para ratio of water desorbed from ice at 10 kelvin.

The anomalously low ortho-to-para ratios (OPRs) exhibited by gaseous water in space have been used to determine the formation temperature (<50 kelvin) of ice on cold interstellar dust. This approach assumes that the OPR of water desorbed from ice is related to the ice formation temperature on the dust. However, we report that water desorbed from ice at 10 kelvin shows a statistical high-temperature OPR of 3, even when the ice is produced in situ by hydrogenation of O2, a known formation process of interstellar water. This invalidates the assumed relation between OPR and temperature. The necessary reinterpretation of the low OPRs will help elucidate the chemical history of interstellar water from molecular clouds and processes in the early solar system, including comet formation.

Quantum tunneling observed without its characteristic large kinetic isotope effects.

Classical transition-state theory is fundamental to describing chemical kinetics; however, quantum tunneling is also important in explaining the unexpectedly large reaction efficiencies observed in many chemical systems. Tunneling is often indicated by anomalously large kinetic isotope effects (KIEs), because a particle's ability to tunnel decreases significantly with its increasing mass. Here we experimentally demonstrate that cold hydrogen (H) and deuterium (D) atoms can add to solid benzene by tunneling; however, the observed H/D KIE was very small (1-1.5) despite the large intrinsic H/D KIE of tunneling (≳ 100). This strong reduction is due to the chemical kinetics being controlled not by tunneling but by the surface diffusion of the H/D atoms, a process not greatly affected by the isotope type. Because tunneling need not be accompanied by a large KIE in surface and interfacial chemical systems, it might be overlooked in other systems such as aerosols or enzymes. Our results suggest that surface tunneling reactions on interstellar dust may contribute to the deuteration of interstellar aromatic and aliphatic hydrocarbons, which could represent a major source of the deuterium enrichment observed in carbonaceous meteorites and interplanetary dust particles. These findings could improve our understanding of interstellar physicochemical processes, including those during the formation of the solar system.