Hiroki Nada

Accessing crystal phases under nonequilibrium conditions is a central challenge for expanding the landscape of materials. Simple-cubic (sc) structures are considered energetically unfavorable in elemental solids and have previously been confirmed only in polonium. Here, we report the direct observation of a previously unrecognized sc-Ag formed under far-from-equilibrium conditions. Using electron beam irradiation inside a high-resolution transmission electron microscope as a trigger, we induced the radiolytic decomposition of silver iodide (AgI) and tracked the in situ formation of silver crystals in real time. Continuous imaging revealed that sc-Ag formation strongly depends on the polymorph of the precursor and occurs selectively from metastable γ-AgI. The sc-Ag exhibited unusually high chemical reactivity, undergoing gradual oxidation into silver oxide under high-vacuum conditions where conventional fcc-Ag remains stable. These findings demonstrate that irreversible crystal formation pathways can kinetically stabilize crystal structures inaccessible under near-equilibrium conditions and extend a previously inaccessible structural limit of metallic bonding.

Crystal polymorphism of complex liquids plays a crucial role in industrial crystallization, food technology, pharmaceuticals, and materials engineering. However, the experimental identification of unknown crystal structures can be challenging, particularly for high-viscosity complex liquids, such as ionic liquids (ILs). In this study, we performed a molecular dynamics simulation coupled with metadynamics to investigate an imidazolium IL (1-alkyl-3-methylimidazolium hexafluorophosphates). The simulation employed two distinct radial-distribution functions, represented by Gaussian window functions as collective variables, and revealed at least two crystal-like phases distinct from the known α and β crystal phases typically formed by this IL. Additionally, the simulation unveiled a unique phase characterized by the ordered spatial arrangement of anion aggregations. These crystal-like and unique phases emerged regardless of the potential used. The simulation methodology presented here is broadly applicable for exploring unknown phases in complex systems and contributes to the design of functional materials, such as porous ILs for gas molecule capture and separation.

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.

Many chemical reactions go through a cascade of events in which a series of metastable intermediates appear, and crystal nucleation is no exception. Although the consensus on the energetics of nucleation suggests the formation of metastable states preceding the crystal growth, little experimental evidence has been reported for their dynamics at an atomistic level. Operando imaging of two-dimensional nucleation on a defect-free NaCl nanocrystal in carbon nanotubes using a millisecond angstrom-resolution transmission electron microscope revealed the formation of a metastable "floating island" (FI) that migrates thermally on the (100) facet of NaCl as the first intermediate of epitaxy. The speed of the migration at 298 K is estimated to be larger than 0.3 nm ms^-1. When a crystal tumbles in a container, a space repeatedly forms between the crystal and the container wall that hosts the FI. Tumbling changes the surface energy repeatedly and promotes the conversion of the FI into a new epitaxial layer. We anticipate that this surface catalysis mechanism found on the nanoscale also operates in bulk heterogeneous nucleation where agitation and attrition accelerate crystallization.

The molecular-scale growth kinetics of ice from water in the presence of air molecules are still poorly understood, despite their importance for understanding ice particle formation in nature. In this study, a molecular dynamics simulation is conducted to elucidate the molecular-scale growth kinetics at the interface between a (111) plane of cubic ice and water in the presence of N₂ molecules. Two potential models of N₂ molecules with and without atomic charges are examined. For both models, N₂ molecules bind stably to the interface for a period of 1 ns or longer, and the stability of the binding is higher for the charged model than for the noncharged model. Free-energy surfaces of an N₂ molecule along the interface and along an ideal (111) plane surface of cubic ice suggest that for both models, the position where an N₂ molecule binds stably is different at the interface and on the ideal plane surface, and the stability of the binding is much higher for the interface than for the ideal plane surface. For both models, stacking-disordered ice grows at the interface, and the formation probability of a hexagonal ice layer in the stacking-disordered ice is higher for the charged model than for the uncharged model. The formation probability for the hexagonal ice layer in the stacking-disordered ice depends not only on the stability of binding but also on the positions where N₂ molecules bind to the underlying ice and the number of N₂ molecules that bind stably to the underlying ice.

Elucidating the stable binding conformations of additives at the surface of CaCO₃ crystals is essential to biomineralization, scale inhibition, and materials technology. However, accomplishing this by experimental means is rather difficult. In this study, molecular dynamics simulations based on a metadynamics approach were conducted to elucidate the stable binding conformations of a deprotonated polymaleic acid (PMA) additive and two deprotonated poly(acrylic acid) (PAA) additives with different polymerization degrees in the presence of various countercations at a hydrated calcite (104) surface. The simulated free-energy surfaces suggested the existence of several slightly different stable binding conformations for each additive. The appearance of these distinct binding conformations is speculated to originate from different balances of interactions between the additive, the calcite surface, and the countercations. The binding conformations and binding stabilities at the calcite surface were affected by the countercations, with Ca²⁺ ions producing a more pronounced effect than Na⁺ ions. Furthermore, the simulation results suggested that the binding stability at the calcite surface was higher for the PMA additive than for the PAA additives, and the PAA additive with a polymerization degree of 10 displayed a binding stability that was similar to or lower than that of the PAA additive with a polymerization degree of 5. The present simulation method provides a new strategy for analyzing the binding conformations of complex additives at material surfaces, developing additives that stably bind to these surfaces, and designing additives to control crystal growth.

Experimental confirmation of liquid polymorphs of water, high-density liquid (HDL) and low-density liquid (LDL), is desired for understanding not only the liquid state of matter but also the origin of the mysterious properties of water. However, this remains challenging because the liquid-liquid critical point of water lies in experimentally inaccessible supercooling conditions known as "no man's land". Here, we show by in situ optical microscopy that droplets and layers of low- and high-density unknown waters (LDUW and HDUW) appear macroscopically depending upon ice polymorphs at non-equilibrium interfaces between water and ices under experimentally accessible (de)pressurization conditions. These unknown waters were found to have characteristic velocities (about 20 and 100 m/s for LDUW and HDUW, respectively) different from water (about 40 m/s) and quasi-liquid layers (QLLs) (about 2 and 0.2 m/s for droplet and layer forms of QLLs, respectively). Our discoveries provide insight on liquid polymorphism of water.

Crystallization is the process of atoms or molecules forming an organized solid via nucleation and growth. Being intrinsically stochastic, the research at an atomistic level has been a huge experimental challenge. We report herein in situ detection of a crystal nucleus forming during nucleation/growth of a NaCl nanocrystal, as video recorded in the interior of a vibrating conical carbon nanotube at 20–40 ms frame^–1 with localization precision of <0.1 nm. We saw NaCl units assembled to form a cluster fluctuating between featureless and semiordered states, which suddenly formed a crystal. Subsequent crystal growth at 298 K and shrinkage at 473 K took place also in a stochastic manner. Productive contributions of the graphitic surface and its mechanical vibration have been experimentally indicated.