First-order Melting Transition Research Articles

Polyhexatic and polycrystalline states of skyrmion lattices

Abstract We report Monte Carlo studies of lattices of up to $10^{5}$ skyrmions treated as particles with negative core energy and repulsive interaction obtained from a microscopic spin model. Temperature dependence of translational and orientational correlations has been investigated for different experimental protocols and initial conditions. Cooling the skyrmion liquid from fully disordered high-temperature state results in the formation of a skyrmion polycrystal. A perfect skyrmion lattice prepared at $T=0$, on raising temperature undergoes a first-order melting transition into a polyhexatic state that consists of large orientationally ordered domains of fluctuating shape. On the further increasing temperature, these domains decrease in size, leading to a fully disordered liquid of skyrmions.

DNA Melting in Poor Solvent

The melting phase diagram of a double-stranded DNA in poor solvent, which promotes condensation, is studied using the pruned and enriched Rosenbluth method on a simple cubic lattice. For slightly poor solvent, melting temperature decreases linearly with a change in the solvent quality, which later changes slope and starts increasing as the melting line approaches the tricritical collapse curve. First-order melting transition, as in good solvent, gives way to continuous transition, and then to further broadened transitions where the order parameter smoothly becomes zero, for sufficiently poor solvent. This change in the melting behavior is accompanied by a continuously varying critical exponent along the second-order transition line, hinting at a non-universal nature of the melting transition. Further, we show that an unbound phase can be achieved just by changing the solvent quality. Importantly, our results conform to the experimental findings qualitatively.

Control of chiral orbital currents in a colossal magnetoresistance material.

Colossal magnetoresistance (CMR) is an extraordinary enhancement of the electrical conductivity in the presence of a magnetic field. It is conventionally associated with a field-induced spin polarization that drastically reduces spin scattering and electric resistance. Ferrimagnetic Mn3Si2Te6 is an intriguing exception to this rule: it exhibits a seven-order-of-magnitude reduction in ab plane resistivity that occurs only when a magnetic polarization is avoided1,2. Here, we report an exotic quantum state that is driven by ab plane chiral orbital currents (COC) flowing along edges of MnTe6 octahedra. The c axis orbital moments of ab plane COC couple to the ferrimagnetic Mn spins to drastically increase the ab plane conductivity (CMR) when an external magnetic field is aligned along the magnetic hard c axis. Consequently, COC-driven CMR is highly susceptible to small direct currents exceeding a critical threshold, and can induce a time-dependent, bistable switching that mimics a first-order 'melting transition' that is a hallmark of the COC state. The demonstrated current-control of COC-enabled CMR offers a new paradigm for quantum technologies.

Thermodynamics of Melting in Colloids and Helium

Enhanced fluctuations pervade a phase near a transition point. This phenomenon was observed in recent simulations of polyhedral particles, where rod-shaped vacancy defects diffused through a solid phase carrying mass flow. The defects proliferated at the melting point, magnifying the mass flow to liquid proportions. Here, we show that the number of vacancies increases on heating or lowering the pressure, in accordance with Boltzmann statistics, but the Boltzmann equilibrium becomes unstable at a threshold number resulting in the first-order melting transition. The instability is driven by an increase in entropy if the defects repel, or by a reduction in enthalpy if they attract. A corresponding thermodynamic instability occurs in other melting transitions, including in argon, colloids, cryogenic helium and simulations of hard spheres. The statistics of the vacancies explains a long-standing anomaly in the heat capacity of solid helium-4, as well as recent measurements of thermally activated mass flow through solid helium-3. In liquid helium-4, the vacancies conform to Feynman’s atomistic and quantum descriptions of rotons and quantitatively account for associated neutron scattering measurements. Colloids, silicon and sodium also melt ‘re-entrantly’ on elevating the pressure, and we identify quantitative evidence that this transition involves the proliferation of interstitial defects.

Current-induced phase transition of moving vortices in untwinned YBa2Cu3O7−δ single crystals

To study the phase transition of vortices induced by current flow, the electrical resistivity and the voltage–current characteristic have been measured on untwinned YBa2Cu3O7−δ single crystals in a magnetic field parallel to the c axis. Near a first-order melting transition (FOMT) line, the well-known counterclockwise hysteresis of resistivity drop disappears completely above a certain current density while a novel clockwise hysteresis appears just below this resistivity drop. Moreover, the voltage–current characteristic does not show any Ohmic behavior as the current increases near the FOMT line. The obtained results are explained by the current-induced melting of the vortex lattice or smectic similar to an increase in the temperature or the magnetic field.

Synthesis and characterization of bis(amine)palladium(II) carboxylate complexes as precursors of palladium nanoparticles.

The synthesis and characterization of the adducts of n-alkyl amine and palladium n-alkyl carboxylate, [Pd(R2NH2)2(R1COO)2] (R1 = 1, 7, and 11; R2 = 8, 12, and 16), as precursors for the synthesis of palladium nanoparticles (PdNPs) was carried out via differential scanning calorimetry, FT-IR, Raman and UV-Vis spectroscopy, NMR spectroscopy (1H, 13C pulsed field gradient spin-echo (PGSE), and 13C CP-MAS), and powder X-ray diffraction. Pd n-alkyl carboxylates were obtained by a ligand exchange reaction from palladium acetate and the appropriate aliphatic carboxylic acid. It is proposed that carboxyl moieties in the presence of amine ligands are bound to palladium ions via monodentate bonding as opposed to bridging bidentate coordination of pure palladium carboxylate which exists in the form of polymer aggregates. All the studied palladium carboxylate/amine complexes form bilayer lamellar structures and exhibit first-order melting transitions. The evidence presented in this study shows that the phase behavior of bivalent metal carboxylates is mainly controlled by the type of coordination of carboxylate head groups. For n-alkyl carboxylates, linear chain type aggregates replace the trimeric units of Pd acetate. In solution, in the presence of amine, palladium salt aggregates disintegrate and the Pd complex is isolated and stabilized by amine molecules. Using bis(amine) palladium carboxylate adducts as precursors, palladium nanoparticles were fabricated. During high temperature thermolysis, the bis(amine) Pd carboxylate complex decomposes to form small sized Pd nanoparticles. Combining NMR techniques with FTIR spectroscopy, it was possible to follow an original stabilization mechanism. PdNPs are stabilized by weakly interacting long chain aliphatic amide and carboxylic acid derived from the palladium precursor.

Finite Temperature Phase Behavior of Viral Capsids as Oriented Particle Shells.

A general phase plot is proposed for discrete particle shells that allows for thermal fluctuations of the shell geometry and of the inter-particle connectivities. The phase plot contains a first-order melting transition, a buckling transition, and a collapse transition and is used to interpret the thermodynamics of microbiological shells.

First-Order Phase Transition in Liquid Ag to the Heterogeneous G-Phase.

A molten metal is an atomic liquid that lacks directional bonding and is free from chemical ordering effects. Experimentally, liquid metals can be undercooled by up to ∼20% of their melting temperature but crystallize rapidly in subnanosecond time scales at deeper undercooling. To address this limited metastability with respect to crystallization, we employed molecular dynamics simulations to study the thermodynamics and kinetics of the glass transition and crystallization in deeply undercooled liquid Ag. We present direct evidence that undercooled liquid Ag undergoes a first-order configurational freezing transition from the high-temperature homogeneous disordered liquid phase (L) to a metastable, heterogeneous, configurationally ordered state that displays elastic rigidity with a persistent and finite shear modulus, μ. We designate this ordered state as the G-phase and conclude it is a metastable non-crystalline phase. We show that the L-G transition occurs by nucleation of the G-phase from the L-phase. Both the L- and G-phases are metastable because both ultimately crystallize. The observed first-order transition is reversible: the G-phase displays a first-order melting transition to the L-phase at a coexistence temperature, TG,M. We develop a thermodynamic description of the two phases and their coexistence boundary.

Multi-messenger nanoprobes of hidden magnetism in a strained manganite.

The ground-state properties of correlated electron systems can be extraordinarily sensitive to external stimuli, offering abundant platforms for functional materials. Using the multi-messenger combination of atomic force microscopy, cryogenic scanning near-field optical microscopy, magnetic force microscopy and ultrafast laser excitation, we demonstrate both 'writing' and 'erasing' of a metastable ferromagnetic metal phase in strained films of La2/3Ca1/3MnO3 (LCMO) with nanometre-resolved finesse. By tracking both optical conductivity and magnetism at the nanoscale, we reveal how strain-coupling underlies the dynamic growth, spontaneous nanotexture and first-order melting transition of this hidden photoinduced metal. Our first-principles calculations reveal that epitaxially engineered Jahn-Teller distortion can stabilize nearly degenerate antiferromagnetic insulator and ferromagnetic metal phases. We propose a Ginzburg-Landau description to rationalize the co-active interplay of strain, lattice distortions and magnetism nano-resolved here in strained LCMO, thus guiding future functional engineering of epitaxial oxides into the regime of phase-programmable materials.

Event-chain Monte Carlo simulations of the liquid to solid transition of two-dimensional decagonal colloidal quasicrystals

In event-chain Monte Carlo simulations, we model colloidal particles in two dimensions that interact according to an isotropic short-ranged pair potential which supports the two typical length scales present in decagonal quasicrystals. We investigate the assembled structures as we vary the density and temperature. Our special interest is related to the transition from quasicrystal to liquid. In contrast to the KTHNY melting theory for quasicrystals which predicts an intermediate pentahedratic phase, we find a one-step first-order melting transition. However, we discover that the slow relaxation of phasonic flips, i.e. rearrangements of the particles due to additional degrees of freedom in quasicrystals, changes the positional correlation functions, to the extent that structures with long-range orientational correlations, but exponentially decaying positional correlations, are observed.

Spontaneous solid-solid interface melting driven by concentration gradient.

The contact of heterogeneous materials with different atomic structures and concentrations becomes omnipresent in modern materials. The differences across the interface introduce various gradients that could alter thermodynamic and kinetic behaviors of the materials. Here, we report a spontaneous melting of the interface formed by a crystalline metal and an amorphous solid at the temperature below their respective equilibrium melting temperatures. The transformation can even become continuous with disappearance of all known features of the first-order melting transition. We show that the change in the nature of melting in the interface region is caused by random disordering induced by interdiffusing atomic elements or impurities in the crystalline phase and the presence of a strong concentration gradient constrained by the sample geometry.

First-order and continuous melting transitions in two-dimensional Lennard-Jones systems and repulsive disks.

In two-dimensional Lennard-Jones (LJ) systems, a small interval of melting-mode switching occurs below which the melting occurs by first-order phase transitions in lieu of the melting scenario proposed by Kosterlitz, Thouless, Halperin, Nelson, and Young (KTHNY). The extrapolated upper bound for phase coexistence is at density ρ∼0.893 and temperature T∼1.1, both in reduced LJ units. The two-stage KTHNY scenario is restored at higher temperatures, and the isothermal melting scenario is universal. The solid-hexatic and hexatic-liquid transitions in KTHNY theory, even so continuous, are distinct from typical continuous phase transitions in that instead of scale-free fluctuations, they are characterized by unbinding of topological defects, resulting in a special form of divergence of the correlation length: ξ≈exp(b|T-T_{c}|^{-ν}). Here such a divergence is firmly established for a two-dimensional melting phenomenon, providing a conclusive proof of the KTHNY melting. We explicitly confirm that this high-temperature melting behavior of the LJ system is consistent with the melting behavior of the r^{-12} potential and that melting of the r^{-n} potential is KTHNY-like for n≤12 but melting of the r^{-64} potential is first order; similar to hard disks. Therefore we suggest that the melting scenario of these repulsive potentials becomes hard-disk-like for an exponent in the range 12<n<64.

Entropy jump at the first-order vortex phase transition in Bi2Sr2CaCu2O8+δ with columnar defects

Abstract We study the entropy jump associated with the first-order vortex melting transition (FOT) in Bi2Sr2CaCu2O8+δ crystals by means of Hall probe magnetometry. The samples present a diluted distribution of columnar defects (CD) introduced by irradiation with Xe ions. The FOT is detected in ac transmittivity measurements as a paramagnetic peak, the height of which is proportional to the enthalpy difference entailed by the transition. By applying the Clausius-Clapeyron relation, we quantify the evolution of the entropy jump Δs as a function of the FOT temperature, TFOT, in both pristine crystals and crystals with CD. On increasing the density of CD, Δs decreases monotonically with respect to values found in pristine samples. The Δs versus TFOT dependence in the case of pristine samples follows reasonably well the theoretical prediction of dominant electromagnetic coupling for a model neglecting the effect of disorder. The data for samples with a diluted distribution of CD are not properly described by such a theoretical model.

Synthesis and characterization of silver nanoparticles from (bis)alkylamine silver carboxylate precursors

A comparative study of amine and silver carboxylate adducts [R1COOAg-2(R2NH2)] (R1 = 1, 7, 11; R2 = 8, 12) as a key intermediate in NPs synthesis is carried out via differential scanning calorimetry, solid-state FT-infrared spectroscopy, 13C CP MAS NMR, powder X-ray diffraction and X-ray photoelectron spectroscopy, and various solution NMR spectroscopies (1H and 13C NMR, pulsed field gradient spin-echo NMR, and ROESY). It is proposed that carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination as opposed to bridging bidentate coordination of pure silver carboxylates resulting from the formation of dimeric units. All complexes are packed as lamellar bilayer structures. Silver carboxylate/amine complexes show one first-order melting transition. The evidence presented in this study shows that phase behavior of monovalent metal carboxylates are controlled, mainly, by head group bonding. In solution, insoluble silver salt is stabilized by amine molecules which exist in dynamic equilibrium. Using (bis)amine-silver carboxylate complex as precursor, silver nanoparticles were fabricated. During high-temperature thermolysis, the (bis)amine-carboxylate adduct decomposes to produce silver nanoparticles of small size. NPs are stabilized by strongly interacting carboxylate and trace amounts of amine derived from the silver precursor interacting with carboxylic acid. A corresponding aliphatic amide obtained from silver precursor at high-temperature reaction conditions is not taking part in the stabilization. Combining NMR techniques with FTIR, it was possible to follow an original stabilization mechanism.Graphical abstractThe synthesis of a series (bis)alkylamine silver(I) carboxylate complexes in nonpolar solvents were carried out and fully characterized both in the solid and solution. Carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination. The complexes form layered structures which thermally decompose forming nanoparticles stabilized only by aliphatic carboxylates.

Two-dimensional melting of colloids with long-range attractive interactions.

The solid-liquid melting transition in a two-dimensional (2-D) attractive colloidal system is visualized using superparamagnetic colloids that interact through a long-range isotropic attractive interaction potential, which is induced using a high-frequency rotating magnetic field. Various experiments, supported by Monte Carlo simulations, are carried out over a range of interaction potentials and densities to determine structure factors, Lindermann parameters, and translational and orientational order parameters. The system shows a first-order solid-liquid melting transition. Simulations and experiments suggest that dislocations and disclinations simultaneously unbind during melting. This is in direct contrast with reports of 2-D melting of paramagnetic particles that interact with a repulsive interaction potential.

Tilted vortex lattice in irradiate Bi2Sr2CaCu2O8+δ single crystals

In order to enlighten the structure of vortex matter in irradiated layered Bi2Sr2CaCu2O8+δ single crystals, the interaction of Josephson vortices and pancake vortices in was investigated by means of the local ac-magnetic permeability measurements by using the miniature local coils, while vortex matter in pristine crystals was studied by in-plane resistivity measurements. The transition anomaly, separating the strong pinning phase and the weak pinning vortex phase was found by both techniques deep in the vortex solid phase solid near ab-plane, indicating crossover from the vortex chains + lattice phase to tilted vortex chains phase. While the columnar defects affect strongly the first-order vortex-lattice melting transition, the magnetic permeability anomaly, associated with the crossover from vortex chains + lattice phase to tilted lattice, is surprisingly still clear, deep in the vortex solid phase. However, the stronger columnar defects eventually affect the crossover anomaly that it disappears too.

Random pinning changes the melting scenario of a two-dimensional core-softened potential system.

In experiments two-dimensional systems are realized mainly on solid substrates, which introduce quenched disorder due to some inherent defects. The defects of substrates influence the melting scenario of the systems and have to be taken into account in the interpretation of experimental results. We present the results of molecular dynamics simulations of a two-dimensional system with a core-softened potential in which a small fraction of the particles is pinned, inducing quenched disorder. Ppotentials of this type are widely used for the qualitative description of systems with waterlike anomalies. In our previous publications it was shown that the system demonstrates an anomalous melting scenario: at low densities the system melts through two continuous transitions in accordance with the Kosterlitz-Thouless-Halperin-Nelson-Young (KTHNY) theory with an intermediate hexatic phase, while at high densities the conventional first-order melting transition takes place. We find that the well-known disorder-induced widening of the hexatic phase occurs at low densities, while in the high-density part of the phase diagram random pinning transforms the first-order melting into two transitions: a continuous KTHNY-like solid-hexatic transition and a first-order hexatic-isotropic liquid transition.

Fluctuation effects in rotating Bose-Einstein condensates with broken SU(2) andU(1)×U(1)symmetries in the presence of intercomponent density-density interactions

Thermal fluctuations and melting transitions for rotating single-component superfluids have been intensively studied and are well understood. In contrast, the thermal effects on vortex states for two-component superfluids with density-density interaction, which have a much richer variety of vortex ground states, have been much less studied. Here, we investigate the thermal effects on vortex matter in superfluids with $\mathrm{U}(1)\ifmmode\times\else\texttimes\fi{}\mathrm{U}(1)$ broken symmetries and intercomponent density-density interactions, as well as the case with a larger $\mathrm{SU}(2)$ broken symmetry obtainable from the $[\mathrm{U}(1)\ifmmode\times\else\texttimes\fi{}\mathrm{U}(1)]$-symmetric case by tuning scattering lengths. In the former case we find that, in addition to first-order melting transitions, the system exhibits thermally driven phase transitions between square and hexagonal lattices. Our main result, however, concerns the case where the condensate exhibits $\mathrm{SU}(2)$ symmetry, and where vortices are not topological. At finite temperature, the system exhibits effects which do not have a counterpart in single-component systems. Namely, it has a state where thermally averaged quantities show no regular vortex lattice, yet the system retains superfluid coherence along the axis of rotation. In such a state, the thermal fluctuations result in transitions between different (nearly) degenerate vortex states without undergoing a melting transition. Our results apply to multicomponent Bose-Einstein condensates, and we suggest how to detect some of these unusual effects experimentally in such systems.

Nature of two-dimensional melting in simple atomic systems

We investigate the characteristics of two-dimensional melting in simple atomic systems via isobaric-isothermal (NPT) and isochoric-isothermal (NV T) molecular dynamics simulations with a special focus on the effect of the range of the potential on the melting. We find that the system with an interatomic potential of longer range clearly exhibits a region (in the PT plane) with a (thermodynamically) stable hexatic phase. On the other hand, the system with a shorter-range potential exhibits a first-order melting transition both in the NPT and the NV T ensembles. Melting of the system with an intermediate range potential shows a hexatic-like feature near the melting transition in the NV T ensemble, but it undergoes an unstable hexatic-like phase during melting process in the NPT ensemble, which implies the existence of a weakly first-order transition. The overall features represent a crossover from a continuous melting transition in the cases of longer-ranged potentials to a discontinuous (first-order) one in the systems with shorter and intermediate ranged potentials. We also calculate the Binder cumulants, as well as the susceptibility, of the bond-orientational order parameter.

Studies of nanocomposites of carbon nanotubes and a negative dielectric anisotropy liquid crystal

It has been widely recognized that the combination of carbon nanotube (CNT) and liquid crystals (LCs) not only provides a useful way to align CNTs, but also dramatically enhances the order in the LC phases, which is especially useful in liquid crystal display (LCD) technology. As the measure of this phase behavior, the complex specific heat is presented over a wide temperature range for a negative dielectric anisotropy alkoxyphenylbenzoate liquid crystal (9OO4) and CNT composites as a function of CNT concentration. The calorimetric scans were performed under near-equilibrium conditions between 25 and 95 °C, first cooling and then followed by heating for CNT weight percent ranging from ϕ(w) = 0 to 0.2. All 9OO4/CNT mesophases have transition temperatures ~1 K higher and a crystallization temperature 4 K higher than that of the pure 9OO4. The crystal phase superheats until a strongly first-order specific heat feature is observed, 0.5 K higher than in the pure 9OO4. The transition enthalpy for the nanocomposite mesophases is 10% lower than that observed in the pure 9OO4. The strongly first-order crystallization and melting transition enthalpies are essentially constant over this range of ϕ(w). Complementary electroclinic measurement on a 0.05 wt. % sample, cooling towards the smectic-C phase from the smectic-A, indicates that the SmA-SmC transition remains mean-field-like in the presence of the CNTs. Given the homogeneous and random distribution of CNTs in these nanocomposites, we interpret these results as arising from the LC-CNT surface interaction pinning the orientational order uniformly along the CNT, without pinning the position of the 9OO4 molecule, leading to a net ordering effect for all phases. These effects of incorporating CNTs into LCs are likely due to "anisotropic orientational" coupling between CNT and LC, the change in the elastic properties of composites and thermal anisotropic properties of the CNTs.