Crystal Nucleation in Supercooled Atomic Liquids.

The liquid-to-solid phase transition is a complex process that is difficult to investigate experimentally with sufficient spatial and temporal resolution. A key aspect of the transition is the formation of a critical seed of the crystalline phase in a supercooled liquid, that is, a liquid in a metastable state below the melting temperature. This stochastic process is commonly described within the framework of classical nucleation theory, but accurate tests of the theory in atomic and molecular liquids are challenging. Here, we employ femtosecond x-ray diffraction from microscopic liquid jets to study crystal nucleation in supercooled liquids of the rare gases argon and krypton. Our results provide stringent limits to the validity of classical nucleation theory in atomic liquids, and offer the long-sought possibility of testing nonclassical extensions of the theory.

Observation of a single protein by ultrafast X-ray diffraction.

The idea of using ultrashort X-ray pulses to obtain images of single proteins frozen in time has fascinated and inspired many. It was one of the arguments for building X-ray free-electron lasers. According to theory, the extremely intense pulses provide sufficient signal to dispense with using crystals as an amplifier, and the ultrashort pulse duration permits capturing the diffraction data before the sample inevitably explodes. This was first demonstrated on biological samples a decade ago on the giant mimivirus. Since then, a large collaboration has been pushing the limit of the smallest sample that can be imaged. The ability to capture snapshots on the timescale of atomic vibrations, while keeping the sample at room temperature, may allow probing the entire conformational phase space of macromolecules. Here we show the first observation of an X-ray diffraction pattern from a single protein, that of Escherichia coli GroEL which at 14 nm in diameter is the smallest biological sample ever imaged by X-rays, and demonstrate that the concept of diffraction before destruction extends to single proteins. From the pattern, it is possible to determine the approximate orientation of the protein. Our experiment demonstrates the feasibility of ultrafast imaging of single proteins, opening the way to single-molecule time-resolved studies on the femtosecond timescale.

N-Electron Valence Perturbation Theory with Reference Wave Functions from Quantum Computing: Application to the Relative Stability of Hydroxide Anion and Hydroxyl Radical.

Quantum simulations of the hydroxide anion and hydroxyl radical are reported, employing variational quantum algorithms for near-term quantum devices. The energy of each species is calculated along the dissociation curve, to obtain information about the stability of the molecular species being investigated. It is shown that simulations restricted to valence spaces incorrectly predict the hydroxyl radical to be more stable than the hydroxide anion. Inclusion of dynamical electron correlation from nonvalence orbitals is demonstrated, through the integration of the variational quantum eigensolver and quantum subspace expansion methods in the workflow of N-electron valence perturbation theory, and shown to correctly predict the hydroxide anion to be more stable than the hydroxyl radical, provided that basis sets with diffuse orbitals are also employed. Finally, we calculate the electron affinity of the hydroxyl radical using an aug-cc-pVQZ basis on IBM's quantum devices.

Characterizing crystalline defects in single nanoparticles from angular correlations of single-shot diffracted X-rays.

Characterizing and controlling the uniformity of nanoparticles is crucial for their application in science and technology because crystalline defects in the nanoparticles strongly affect their unique properties. Recently, ultra-short and ultra-bright X-ray pulses provided by X-ray free-electron lasers (XFELs) opened up the possibility of structure determination of nanometre-scale matter with Å spatial resolution. However, it is often difficult to reconstruct the 3D structural information from single-shot X-ray diffraction patterns owing to the random orientation of the particles. This report proposes an analysis approach for characterizing defects in nanoparticles using wide-angle X-ray scattering (WAXS) data from free-flying single nanoparticles. The analysis method is based on the concept of correlated X-ray scattering, in which correlations of scattered X-ray are used to recover detailed structural information. WAXS experiments of xenon nanoparticles, or clusters, were conducted at an XFEL facility in Japan by using the SPring-8 Ångstrom compact free-electron laser (SACLA). Bragg spots in the recorded single-shot X-ray diffraction patterns showed clear angular correlations, which offered significant structural information on the nanoparticles. The experimental angular correlations were reproduced by numerical simulation in which kinematical theory of diffraction was combined with geometric calculations. We also explain the diffuse scattering intensity as being due to the stacking faults in the xenon clusters.

Crystal growth rates in supercooled atomic liquid mixtures.

Crystallization is a fundamental process in materials science, providing the primary route for the realization of a wide range of new materials. Crystallization rates are also considered to be useful probes of glass-forming ability1-3. At the microscopic level, crystallization is described by the classical crystal nucleation and growth theories4,5, yet in general solid formation is a far more complex process. In particular, the observation of apparently different crystal growth regimes in many binary liquid mixtures greatly challenges our understanding of crystallization1,6-12. Here, we study by experiments, theory and computer simulations the crystallization of supercooled mixtures of argon and krypton, showing that crystal growth rates in these systems can be reconciled with existing crystal growth models only by explicitly accounting for the non-ideality of the mixtures. Our results highlight the importance of thermodynamic aspects in describing the crystal growth kinetics, providing a substantial step towards a more sophisticated theory of crystal growth.

Ultrafast Structural Dynamics of Nanoparticles in Intense Laser Fields.

Femtosecond laser pulses have opened new frontiers for the study of ultrafast phase transitions and nonequilibrium states of matter. In this Letter, we report on structural dynamics in atomic clusters pumped with intense near-infrared (NIR) pulses into a nanoplasma state. Employing wide-angle scattering with intense femtosecond x-ray pulses from a free-electron laser source, we find that highly excited xenon nanoparticles retain their crystalline bulk structure and density in the inner core long after the driving NIR pulse. The observed emergence of structural disorder in the nanoplasma is consistent with a propagation from the surface to the inner core of the clusters.

Novel behavior of monolayer quantum gases on graphene, graphane and fluorographene.

This article discusses the behavior of submonolayer quantum films (He and H2) on graphene and newly discovered surfaces that are derived from graphene. Among these substrates are graphane (abbreviated GH), which has an H atom bonded to each C atom, and fluorographene (GF). The subject is introduced by describing the related problem of monolayer films on graphite. For that case, extensive experimental and theoretical investigations have revealed that the phase diagrams of the Bose gases (4)He and para-H2 are qualitatively similar, differing primarily in a higher characteristic temperature scale for H2 than for He. The phase behavior of these films on one side of pristine graphene, or both sides of free-standing graphene, is expected to be similar to that on graphite. We point out the possibility of novel phenomena in adsorption on graphene related to the large flexibility of the graphene sheet, to the non-negligible interaction between atoms adsorbed on opposite sides of the sheet and to the perturbation effect of the adsorbed layer on the Dirac electrons. In contrast, the behavior predicted on GF and GH surfaces is very different from that on graphite, a result of the different corrugation, i.e., the lateral variation of the potential experienced by these gases. This arises because on GF, for example, half of the F atoms are located above the C plane while the other half are below this plane. Hence, the He and H2 gases experience very different potentials from those on graphite or graphene. As a result of this novel geometry and potential, distinct properties are observed. For example, the (4)He film's ground state on graphite is a two-dimensional (2D) crystal commensurate with the substrate, the famous [Formula: see text] phase; on GF and GH, instead, it is predicted to be an anisotropic superfluid. On GF the anisotropy is so extreme that the roton excitations are very anisotropic, as if the bosons are moving in a multiconnected space along the bonds of a honeycomb lattice. Such a novel phase has not been predicted or observed previously on any substrate. Also, in the case of (3)He the film's ground state is a fluid, thus offering the possibility of studying an anisotropic Fermi fluid with a tunable density. The exotic properties expected for these films are discussed along with proposed experimental tests.