Structural and electronic changes in Ga-In and Ga-Sn alloys on melting.

The melting behaviour of surface slabs of Ga-In and Ga-Sn is studied using periodic density functional theory and ab initio molecular dynamics. Analysis of the structure and electronics of the solid and liquid phases gives insight into the properties of these alloys, and why they may act as promising CO2 reduction catalysts. We report melting points for slabs of hexa-layer Ga-In (386 K) and Ga-Sn (349 K) that are substantially lower than the pure hexa-layer Ga system (433 K), and attribute the difference to the degree to which the dopant (In or Sn) disrupts the layered Ga network. In molecular dynamics trajectories of the liquid structures, we find that dopant tends to migrate from the centre of the slab towards the surface and accumulate there. Bader charge calculations reveal that the surface dopant atoms have increased positive charge, and density of states analyses suggest the liquid alloys maintain metallic electronic behaviour. Thus, surface In and Sn may provide good binding sites for intermediates in CO2 reduction. This work contributes to our understanding of the properties of liquid metal systems, and provides a foundation for modelling catalysis on these materials.

Dynamic Activation of Ga Sites by Pt Dopant in Low-Temperature Liquid-Metal Catalysts.

Liquid GaPt catalysts with Pt concentrations as low as 1×10-4  atomic % have recently been identified as highly active for the oxidation of methanol and pyrogallol under mild reaction conditions. However, almost nothing is known about how liquid state catalysts support these significant improvements in activity. Here, ab initio molecular dynamics simulations are employed to examine GaPt catalysts in isolation and interacting with adsorbates. We find that persistent geometric features can exist in the liquid state, given the correct environment. We postulate that the Pt dopant may not be limited to direct involvement in catalysis of reactions, but rather that its presence can also enable Ga atoms to become catalytically active.

A mechanistic understanding of surface Bi enrichment in dilute GaBi systems.

Experiment has shown that dilute GaBi systems produce a range of self-organised nanostructured patterns at the surface [Tang et al., Nat. Nanotechnol., 2021, 16, 431-439]. Using extensive ab initio molecular dynamics simulations, we elucidate the mechanisms underlying the formation of the Bi surface islands in Bi-doped Ga liquid metals. Here, we show that in order for internal Bi atoms to diffuse to the surface a lateral extension of the Ga surface network is required. Furthermore, the absence of surface Bi patterning perturbs the Ga surface network providing a preferred path for an internal Bi to diffuse. By understanding how and why Bi nucleates at a surface, we increase the ability to control, manipulate and design such systems for use in future electronic devices.

Clustering of metal dopants in defect sites of graphene-based materials.

Single-atom catalysts are promising candidates for many industrial reactions. However, making true single-atom catalysts is an experimental dilemma, due to the difficulty of keeping dopant single atoms stable at temperature and under pressure. This difficulty can lead to clustering of the metal dopant atoms in defect sites. However, the electronic and geometric structure of sub-nanoscale clusters in single-atom defects has not yet been explored. Furthermore, recent studies have proven sub-nanoscale clusters of dopants in single-atom defect sites can be equally good or better catalysts than their single-atom counterparts. Here, a comprehensive DFT study is undertaken to determine the geometric and electronic structure effects that influence clustering of noble and p-block dopants in C3- and N4-defect sites in graphene-based systems. We find that the defect site is the primary driver in determining clustering dynamics in these systems.

A Two-Dimensional Liquid Structure Explains the Elevated Melting Temperatures of Gallium Nanoclusters.

Melting in finite-sized materials differs in two ways from the solid-liquid phase transition in bulk systems. First, there is an inherent scaling of the melting temperature below that of the bulk, known as melting point depression. Second, at small sizes changes in melting temperature become nonmonotonic and show a size-dependence that is sensitive to the structure of the particle. Melting temperatures that exceed those of the bulk material have been shown to occur for a very limited range of nanoclusters, including gallium, but have still never been ascribed a convincing physical explanation. Here, we analyze the structure of the liquid phase in gallium clusters based on molecular dynamics simulations that reproduce the greater-than-bulk melting behavior observed in experiments. We observe persistent nonspherical shape distortion indicating a stabilization of the surface, which invalidates the paradigm of melting point depression. This shape distortion suggests that the surface acts as a constraint on the liquid state that lowers its entropy relative to that of the bulk liquid and thus raises the melting temperature.

Quantum size effects in the size-temperature phase diagram of gallium: structural characterization of shape-shifting clusters.

Finite temperature analysis of cluster structures is used to identify signatures of the low-temperature polymorphs of gallium, based on the results of first-principle Born-Oppenheimer molecular dynamics simulations. Pre-melting structural transitions proceed from either the ß- and/or the δ-phase to the γ- or δ-phase, with a size- dependent phase progression. We relate the stability of each isomer to the electronic structures of the different phases, giving new insight into the origin of polymorphism in this complicated element.

Dense or porous packing? Two-dimensional self-assembly of star-shaped mono-, bi-, and terpyridine derivatives.

The self-assembly behavior of five star-shaped pyridyl-functionalized 1,3,5-triethynylbenzenes was studied at the interface between an organic solvent and the basal plane of graphite by scanning tunneling microscopy. The mono- and bipyridine derivatives self-assemble in closely packed 2D crystals, whereas the derivative with the more bulky terpyridines crystallizes with porous packing. DFT calculations of a monopyridine derivative on graphene, support the proposed molecular model. The calculations also reveal the formation of hydrogen bonds between the nitrogen atoms and a hydrogen atom of the neighboring central unit, as a small nonzero tunneling current was calculated within this region. The title compounds provide a versatile model system to investigate the role of multivalent steric interactions and hydrogen bonding in molecular monolayers.

Al20(+) does melt, albeit above the bulk melting temperature of aluminium.

Employing first principles parallel tempering molecular dynamics in the microcanonical ensemble, we report the presence of a clear solid-liquid-like melting transition in Al20(+) clusters, not found in experiments. The phase transition temperature obtained from the multiple histogram method is 993 K, 60 K above the melting point of aluminium. Root mean squared bond length fluctuation, the velocity auto-correlation function and the corresponding power spectrum further confirm the phase transition from a solid-like to liquid-like phase. Atoms-In-Molecules analysis shows a strong charge segregation between the internal and surface atoms, with negatively charged internal atoms and positive charge at the surface. Analysis of the calculated diffusion coefficients indicates different mobilities of the internal and surface atoms in the solid-like phase, and the differences between the environment of the internal atoms in these clusters with that of the bulk atoms suggest a physical picture for the origin of greater-than-bulk melting temperatures.

Method of increments for the halogen molecular crystals: Cl, Br, and I.

Method of increments (MI) calculations reveal the n-body correlation contributions to binding in solid chlorine, bromine, and iodine. Secondary binding contributions as well as d-correlation energies are estimated and compared between each solid halogen. We illustrate that binding is entirely determined by two-body correlation effects, which account for >80% of the total correlation energy. One-body, three-body, and exchange contributions are repulsive. Using density-fitting (DF) local coupled-cluster singles, doubles, and perturbative triples for incremental calculations, we obtain excellent agreement with the experimental cohesive energies. MI results from DF local second-order Møller-Plesset perturbation (LMP2) yield considerably over-bound cohesive energies. Comparative calculations with density functional theory and periodic LMP2 method are also shown to be less accurate for the solid halogens.

Resolving decades of debate: the surprising role of high-temperature covalency in the structure of liquid gallium.

Liquid metals (LMs) have the potential to revolutionise many important technologies, ranging from battery components to catalytic reactions. Low melting temperature gallium (Ga) is particularly promising as a solvent in many LM alloys, due to the low energy cost of maintaining its liquid state. However, despite 30+ years of study on the nature of Ga's liquid structure, it remains enigmatic with significant disagreement among the many published reports. In this work, we reconcile many of the conflicts through analysis of extensive ab initio molecular dynamics simulations of bulk Ga liquid at different temperatures. Contrary to previous assumptions, covalency becomes more important in the liquid at higher temperatures, meaning that covalency is not a significant feature of the liquid near the phase transition temperature. This explains the experimental observation of a decrease of resistivity of the metal upon melting, and its subsequent anomalously nonlinear increase with temperature. This revised understanding of structuring in the liquid has implications for the way these alloys are tailored for specific applications in the rapidly developing field of LMs.

First-principles melting of gallium clusters down to nine atoms: structural and electronic contributions to melting.

First-principles Born-Oppenheimer molecular dynamics simulations of small gallium clusters, including parallel tempering, probe the distinction between cluster and molecule in the size range of 7-12 atoms. In contrast to the larger sizes, dynamic measures of structural change at finite temperature demonstrate that Ga7 and Ga8 do not melt, suggesting a size limit to melting in gallium exists at 9 atoms. Analysis of electronic structure further supports this size limit, additionally demonstrating that a covalent nature cannot be identified for clusters larger than the gallium dimer. Ga9, Ga10 and Ga11 melt at greater-than-bulk temperatures, with no evident covalent character. As Ga12 represents the first small gallium cluster to melt at a lower-than-bulk temperature, we examine the structural properties of each cluster at finite temperature in order to probe both the origins of greater-than-bulk melting, as well as the significant differences in melting temperatures induced by a single atom addition. Size-sensitive melting temperatures can be explained by both energetic and entropic differences between the solid and liquid phases for each cluster. We show that the lower-than-bulk melting temperature of the 12-atom cluster can be attributed to persistent pair bonding, reminiscent of the pairing observed in α-gallium. This result supports the attribution of greater-than-bulk melting in gallium clusters to the anomalously low melting temperature of the bulk, due to its dimeric structure.

How a single aluminum atom makes a difference to gallium: First-principles simulations of bimetallic cluster melting.

First principles molecular dynamics simulations of Ga19Al(+) have been performed in the microcanonical ensemble using parallel tempering. We perform a thorough investigation of the changes induced by the presence of an Al atom in the Ga dominated cluster. Dynamic analysis indicates that the Al atom prefers to occupy the internal sites of the cluster structure, at all temperatures, and above 450 K, the Al atom is less mobile than the central Ga atom throughout the simulation. Using the multiple histogram method, canonical specific heat curves are obtained that compare well with previous experimental measurements of the specific heat and equivalent simulations for the Ga20 (+) cluster. The first-principles melting temperature agrees well with the experimental value for Ga19Al(+). Analysis of the root mean squared fluctuation in bond length, velocity auto-correlation function, and the corresponding power spectrum, confirms the solid-liquid-like phase transition in Ga19Al(+), as for Ga20 (+).

Dynamic sampling of liquid metal structures for theoretical studies on catalysis.

Liquid metals have recently emerged as promising catalysts that can outcompete their solid counterparts for many reactions. Although theoretical modelling is extensively used to improve solid-state catalysts, there is currently no way to capture the interactions of adsorbates with a dynamic liquid metal. We propose a new approach based on ab initio molecular dynamics sampling of an adsorbate on a liquid catalyst. Using this approach, we describe time-resolved structures for formate adsorbed on liquid Ga-In, and for all intermediates in the methanol oxidation pathway on Ga-Pt. This yields a range of accessible adsorption energies that take into account the at-temperature motion of the liquid metal. We find that a previously proposed pathway for methanol oxidation on Ga-Pt results in unstable intermediates on a dynamic liquid surface, and propose that H desorption must occur during the path. The results showcase a more accurate way to treat liquid metal catalysts in this emerging field.

Concentration dependent alloying behaviour of liquid GaAu.

Liquid GaAu systems provide the possibility of developing dynamic and self-healing materials for a variety of applications, including catalysis. GaAu systems provide both dynamic capability by being liquid at just above room temperature, as a result of the Ga, and likely catalytic activity, resulting from the Au. While the formation of a Ga2Au intermetallic is known, the behaviours that result from lower Au concentrations within a liquid Ga solvent are hitherto unknown. Here, ab initio molecular dynamics are used to understand how different low concentrations of Au operate within a liquid Ga solvent. We determine that Au concentrations of between 15% Au wt and 25% Au wt will give rise to the highest abundance of stabilised single Au atoms.

Liquid metal synthesis solvents for metallic crystals.

In nature, snowflake ice crystals arrange themselves into diverse symmetrical six-sided structures. We show an analogy of this when zinc (Zn) dissolves and crystallizes in liquid gallium (Ga). The low-melting-temperature Ga is used as a "metallic solvent" to synthesize a range of flake-like Zn crystals. We extract these metallic crystals from the liquid metal solvent by reducing its surface tension using a combination of electrocapillary modulation and vacuum filtration. The liquid metal-grown crystals feature high morphological diversity and persistent symmetry. The concept is expanded to other single and binary metal solutes and Ga-based solvents, with the growth mechanisms elucidated through ab initio simulation of interfacial stability. This strategy offers general routes for creating highly crystalline, shape-controlled metallic or multimetallic fine structures from liquid metal solvents.

Modulating the thermal and structural stability of gallenene via variation of atomistic thickness.

Using ab initio molecular dynamics, we show that a recently discovered form of 2D Ga-gallenene-exhibits highly variable thickness dependent properties. Here, 2D Ga of four, five and six atomic layers thick are found to be thermally stable to 457 K, 350 K and 433 K, respectively; all well above that of bulk Ga. Analysis of the liquid structure of 2D Ga shows a thickness dependent ordering both parallel and perpendicular to the Ga/vacuum interface. Furthermore, ground state optimisations of 2D Ga to 12 atomic layers thick shows a return to a bulk-like bonding structure at 10 atoms thick, therefore we anticipate that up to this thickness 2D Ga structures will each exhibit novel properties as discrete 2D materials. Gallenene has exciting potential applications in plasmonics, sensors and electrical contacts however, for the potential of 2D Ga to be fully realised an in depth understanding of its thickness dependent properties is required.

Unique surface patterns emerging during solidification of liquid metal alloys.

It is well-understood that during the liquid-to-solid phase transition of alloys, elements segregate in the bulk phase with the formation of microstructures. In contrast, we show here that in a Bi-Ga alloy system, highly ordered nanopatterns emerge preferentially at the alloy surfaces during solidification. We observed a variety of transition, hybrid and crystal-defect-like patterns, in addition to lamellar and rod-like structures. Combining experiments and molecular dynamics simulations, we investigated the influence of the superficial Bi and Ga2O3 layers during surface solidification and elucidated the pattern-formation mechanisms, which involve surface-catalysed heterogeneous nucleation. We further demonstrated the dynamic nature and robustness of the phenomenon under different solidification conditions and for various alloy systems. The surface patterns we observed enable high-spatial-resolution nanoscale-infrared and surface-enhanced Raman mapping, which reveal promising potential for surface- and nanoscale-based applications.

Ultra stable superatomic structure of doubly magic Ga13 and Ga13Li electrolyte.

We report the extreme thermal stability of the superatomic electronic structure for 13-atom gallium clusters and the Ga13Li electrolyte. Using previously-validated first-principles simulations, [K. G. Steenbergen and N. Gaston, Phys. Rev. B: Condens. Matter Mater. Phys., 2013, 88, 161402-161405] we show that the superatomic shell progression of doubly-magic Ga13- remains stable up to 1000 K, making this cluster an ideal candidate for high-temperature applications requiring an exceptionally stable electronic structure. Using the neutral and cationic clusters for comparison, we quantify the extent to which cluster stability (geometric and electronic) is modified through addition or subtraction of a single electron. Finally, combining 13-atom gallium with lithium, we illustrate that superatomic closed-shell Ga13Li exhibits the same exceptionally high thermal stability as naked Ga13-. For technological use as a superatomic electrolyte, we demonstrate that Ga13Li has a low affinity to water as well as a low Li+ binding energy.

Thickness dependent thermal stability of 2D gallenene.

The recent discovery of two-dimensional (2D) gallium, in the form of metallic gallenene, has added to a long history of interest in the thermodynamic stability and structures of gallium. Despite research suggesting that two-dimensionality and surface stabilisation play an important role in both bulk and nanostructures of gallium, the properties and stability of different forms of 2D structures have remained unexplored. Through extensive density functional theory simulations, we investigate the structure and thermal stability of freestanding bilayer and trilayer gallenene. Our results show that reducing bulk gallium to two dimensions actually enhances the thermal stability. We also discover the origin of this intriguing result.

Accurate, Large-Scale Density Functional Melting of Hg: Relativistic Effects Decrease Melting Temperature by 160 K.

Using first-principles calculations and the "interface pinning" method in large-scale density functional molecular dynamics simulations of bulk melting, we prove that mercury is a liquid at room temperature due to relativistic effects. The relativistic model gives a melting temperature of 241 K, in excellent agreement with the experimental temperature of 234 K. The nonrelativistic melting temperature is remarkably high at 402 K.