Thermodynamic Transition Research Articles

Phase transition face-centered cubic crystal — homogeneous phase in helium

In this work, the characteristics of the phase transition face-centered cubic crystal — homogeneous phase in helium are calculated based on the correlation cell-cluster expansion. The theoretical data were compared with experimental data and good agreement was obtained. It is discussed the use of data on phase transitions in helium to estimate thermodynamic characteristics phase transition in a quantum system of hard spheres.

K-core attack, equilibrium K-core, and kinetically constrained spin system

Abstract Kinetically constrained spin systems are toy models of supercooled liquids and amorphous solids. In this Perspective, we revisit the prototypical Fredrickson-Andersen (FA) kinetically constrained model from the viewpoint of K-core combinatorial optimization. Each kinetic cluster of the FA system, containing all the mutually visitable microscopic occupation configurations, is exactly the solution space of a specific instance of the K-core attack problem. The whole set of different jammed occupation patterns of the FA system is the configuration space of an equilibrium K-core problem. Based on recent theoretical results achieved on the K-core attack and equilibrium K-core problems, we discuss the thermodynamic spin glass phase transitions and the maximum occupation density of the fully unfrozen FA kinetic cluster, and the minimum occupation density and extreme vulnerability of the partially frozen (jammed) kinetic clusters. The equivalence between K-core attack and the fully unfrozen FA kinetic cluster also implies a new way of sampling K-core attack solutions.

Thermodynamic signatures and phase transitions in high-energy Au-Au collisions

Abstract In this study, we systematically investigate the dynamics of various particles namely π+, π−, K+, K−, p, ̄p, Λ, ̄Λ, Ξ− and ̄Ξ+ produced in central Au-Au collisions. We analyze data of AGS and RHIC, which span a broad range of collision energies, ranging from √sN N = 1.9 to 200 GeV. To analyze the transverse momentum (pT ) and transverse mass (mT ) distributions, we employ a two-component standard distribution function, achieving a very good representation of the experimental data across these energy regimes. We extract key thermodynamic parameters, including the effective temperature T , the mean transverse momentum ⟨pT ⟩, and the initial temperature Ti, and analyze their dependence on the values of collision energy and particle mass. Our findings reveal a distinct transition behaviour around √sN N = 19.6 GeV. Below √sN N = 19.6 GeV, the values of T , ⟨pT ⟩, and Ti increase monotonically for all particles due to higher energy transfer into the system. Above this energy threshold, these extracted parameters plateau, suggesting that the additional energy is utilized as latent heat for phase transition rather than increasing the system’s temperature. These observations delineate two distinct regions: a baryon-dominated region at lower energies and a parton-dominated region at higher energies, each potentially indicative of different phases of matter, with the latter possibly signalling the onset of a Quark-Gluon Plasma (QGP). The study thus provides critical insights into the complex interplay of thermodynamics, phase transitions, and particle interactions in high-energy Au-Au collisions.

Nonaggregated Anions Enable the Undercooled Aqueous Electrolyte for Low-Temperature Applications.

Aqueous batteries, with the advantages of high safety and low cost, are highly promising for large-scale energy storage. However, freezing of the aqueous electrolyte limits the low-temperature operation. Here, we propose and achieve a highly dispersed solvation structure in the electrolyte by coupling nonaggregated Cl- anions, which reduces the water cluster size and prevents the solidification of the aqueous electrolyte until -136.3 °C. The low-temperature LiCl electrolyte exhibits a high ionic conductivity (1.0 mS cm-1) at -80 °C and enables a stable low-temperature Ag/AgCl reference electrode at -50 °C. Moreover, the polyaniline-based battery can work at an extremely low temperature of -100 °C and shows superior cycling performance of 4000 cycles at -40 °C with 95.7% capacity retention. This work elucidates the correlation between the anion effect and the thermodynamic transition of the electrolyte, offering a novel approach for designing low-temperature electrolytes.

Phase transition thermodynamics of organic semiconductors: N,N,N’,N’-tetraphenylbenzidine and 4,4′-bis(N-carbazolyl)-1,1′-biphenyl

In this work, we report a comprehensive study of the phase change thermodynamics of two compounds, N,N,N’,N’-tetraphenylbenzidine (TPB) and 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP), used in the production of organic light-emitting diodes and photovoltaics. The vapor pressures and phase transition enthalpies of these compounds have been previously studied at the elevated temperatures which may not be relevant to the conditions during fabrication and use TPB- and CBP-based materials. In this work, a combination of experimental and computational methods was employed to establish the reliable temperature dependences of the sublimation, fusion, and vaporization enthalpies of TPB and CBP in a wide temperature range. The vapor pressures of both compounds over solid and liquid phases were measured using fast scanning calorimetry. The fusion enthalpies at the melting point were determined by DSC. The isobaric heat capacities of the compounds in crystalline and liquid phases, including the supercooled liquids, were measured using scanning calorimetry. For the first time, the heat capacities of the ideal gas TPB and CBP were computed, considering internal rotation effects. The solution enthalpies in benzene at 298.15 K were measured, providing an independent estimate of the fusion enthalpy temperature dependence. Its consistency with the data on the fusion enthalpies was confirmed using Hess’s and Kirchhoff’s laws of Thermochemistry. Using the obtained results, the available literature data were critically evaluated. The obtained thermodynamic parameters may facilitate optimization of vapor deposition conditions and description of the thermodynamic and kinetic stability of the glassy state of TPB and CBP.

Investigation of thermodynamic state evolution, phase transition and mixing of the hydrocarbon droplet in convective supercritical environments

Liquid alkane droplets transit to supercritical fluids under supercritical conditions. However, the subsequent thermodynamic state evolution, phase transition, and mixing in this case, which directly influences combustion in actual diesel engines, need further investigation. We studied the thermodynamic state evolution, phase transition, and mixing of n-heptane droplets in supercritical laminar nitrogen streams through a set of conservation equations. Non-ideal thermodynamic and transport properties were calculated to incorporate the dramatic variation of physical properties in the supercritical regime. We focus on the effects of Reynolds number, ambient pressure, and droplet size on the thermodynamic state evolution, phase transition and mixing of droplets. Results showed that increasing the Reynolds number can accelerate the evolution of thermodynamic states, which leads to the faster transition of droplets from the liquid phase and supercritical fluids to gas-phase mixtures. With the increased Reynolds number, the phase transition rate is increased and the mixing homogeneity is improved due to the enhanced mass transfer. Caused by the negative correlation between mass transfer and ambient pressure, in higher pressure, droplets after the supercritical transition require more time to transition from supercritical fluids to vapor-phase mixtures. Increasing ambient pressure inhibited the droplet phase transition process and deteriorated the mixing homogeneity, but no significant influence was shown on the droplet dynamic evolution process. Smaller droplets transition faster from liquid phase and supercritical fluids to vapor-phase mixtures. The faster thermodynamic state evolution and faster dynamic evolution process of the smaller droplet leads to its more rapid homogeneous mixing with ambient gasses, but the mode of dynamics is independent of the droplet size.

Emergent Properties in Chemistry - Relating Molecular Properties to Bulk Behavior.

Certain properties of an object only emerge when a sufficient number of those objects are present in a definite arrangement. For example, one or two water molecules cannot said to be in a liquid state, but a drop of water can be. This concept of emergence has been studied extensively, but only occasionally discussed explicitly in the context of chemistry. In this paper, we aim to show the fruitfulness of the concept of emergence for chemical inquiry by considering four case studies of emergent chemical properties, i. e., the liquidity and freezing of water, structural properties of crystals, thermodynamical phase transitions and quantum mechanical phenomena. We show that some of these properties emerge gradually, some at discrete points, and some should be taken to emerge only when the number of constituents tends to infinity. We argue that studying the way in which chemical properties emerge presents a useful avenue for research that promises greater insight into the nature of those properties.

Bidirectional tandem catalysis coupled with interface engineering and Se vacancies for accelerating the polysulfide conversion

The shuttling of long-chain LiPSs (Li2Sn, 4 ≤ n ≤ 8) and the sluggish conversion from Li2S4 to Li2S represent two primary challenges hindering the fast multi-step transformations of lithium-sulfur (Li-S) batteries. Here, we propose a bidirectional tandem catalytic strategy to promote polysulfide conversions. A novel nanostructured catalyst consisting of hollow bimetallic selenide (ZnSe/SnSe2) cubes with dual-active centers, heterogeneous interfaces and selenium-rich vacancies was synthesized. Experimental and theoretical calculations confirmed that ZnSe and SnSe2 selectively reduced the thermodynamic transition energy barrier of S8→Li2S4 and Li2S4→Li2S to achieve baton-relay-like conversion of polysulfides. Moreover, the synergistic effect of ZnSe and SnSe2 significantly reduced the activation barrier of Li2S reoxidation during the charging process, and achieved an efficient bidirectional catalytic conversion. In situ Raman analysis confirmed that ZnSe/SnSe2 effectively inhibited the shuttle effect. As a result, a battery with ZnSe/SnSe2 interlayer delivered high specific capacity of 1269.5 mAh g−1 at 0.2 C, and excellent rate capability (680.4 mAh g−1 at 4 C). Remarkably, the battery maintained cycling stability with only 0.086% capacity degradation per cycle after 500 cycles at 2 C. This work provides a new path for designing electrocatalyst towards precise control of catalytic processes in Li-S batteries.

Kinetic and Thermodynamic Transition Pathways of Silica by Machine Learning: Implication for Meteorite Impacts

AbstractRocks falling to Earth from space may generate pressure and temperature approaching Earth's deep mantle, but such meteorite impact only persists for a very short period. Under these extreme conditions, kinetical factors largely control mineral phase transitions, in which the resultant phase may deviate from those at thermal equilibrium. Here, we focus on the phase transitions of silica during meteorite impact, and have elucidated multiple pathways from low‐coordinated silica to seifertite, the densest known silica found in meteorite samples. Utilizing a high‐dimensional neuro‐network potential specifically designed for silica, we exhaustively map the potential energy landscape through stochastic surface walking and uncover low‐barrier transition pathways toward seifertite at pressures far away from thermal equilibrium. These kinetic‐driven transitions are then characterized by first‐principles simulations, revealing narrow transition windows of pressure, with seifertite becoming more kinetically favored over stishovite at pressures in the vicinity of 10 and 25 GPa. Our results suggest that meteorite impacts should have reached such target pressures to overcome the thermodynamic limit of forming seifertite. The presence of seifertite may provide key information in constraining the relevant dynamic compression conditions.

Complex magnetic interactions and critical behavior analysis in quaternary CoFeV0.8Mn0.2Si Heusler alloy

We investigate the magnetic behavior and critical exponents of quaternary CoFeV0.8Mn0.2Si Heusler alloy to understand the interactions across the Curie temperature (TC). The Rietveld refinement of the x-ray diffraction pattern with the space group F4¯3m confirms a single-phase cubic Y-type crystal structure. The magnetic susceptibility χ(T) data show a ferromagnetic nature with a second-order phase transition from paramagnetic to ferromagnetic at 446±1 K. The saturation magnetization at 5 K is found to be 2.2 μB/f.u., which is close to the Slater–Pauling rule and indicates its half-metallic nature. The values of asymptotic critical exponents (β, γ, and δ) and the TC are extracted through detailed analytical analysis including the modified Arrott plot, the Kouvel–Fisher (K–F) method, and the Widom scaling relation. Interestingly, the estimated values of β=0.369 and γ=1.445 closely approximate the theoretical values of the 3D Heisenberg model across the TC and validate the second-order thermodynamic phase transition. The obtained exponents lead to the collapse of renormalized isotherms, represented by the relationship between the magnetization (m) and the applied magnetic field (h), into two distinct branches above and below the TC, which validates the reliability of the analysis. Furthermore, these exponents suggest that the spin interaction follows a decay pattern of J(r)∼r−4.99, indicating a short-range magnetic ordering, akin to the itinerant-electron 3D Heisenberg model.

Effect of Cr/Mn Addition in TiVNb on Hydrogen Sorption Properties: Thermodynamics and Phase Transition Study

High-entropy alloys (HEAs) are a promising class of materials that can grant remarkable functional performances for a large range of applications due to their highly tunable composition. Among these applications, recently, bcc HEAs capable of forming fcc hydrides have been proposed as high-capacity hydrogen storage materials with improved thermodynamics compared to classical metal hydrides. In this context, a single-phase bcc (TiVNb)0.90Cr0.05Mn0.05 HEA was prepared by arc melting to evaluate the effect of combined Cr/Mn addition in the ternary TiVNb. A thermodynamic destabilization of the fcc hydride phase was found in the HEA compared to the initial TiVNb. In situ neutron and synchrotron X-ray diffraction experiments put forward a fcc → bcc phase transition of the metallic subnetwork in the temperature range of 260–350 °C, whereas the H/D subnetwork underwent an order → disorder transition at 180 °C. The absorption/desorption cycling demonstrated very fast absorption kinetics at room temperature in less than 1 min with a remarkable total capacity (2.8 wt.%) without phase segregation. Therefore, the design strategy consisting of small additions of non-hydride-forming elements into refractory HEAs allows for materials with promising properties for solid-state hydrogen storage to be obtained.

Nonextensive entropies impact onto thermodynamics and phase structure of Kerr–Newman black holes

Taking the nonextensive Tsallis and Rényi entropies into account, we explore thermodynamic properties and phase transitions of the Kerr–Newman black holes (KNBH) in the microcanonical and canonical ensembles. We also compare our results with those obtained by attributing the Bekenstein–Hawking entropy bound to the mentioned black holes. Our analysis indicates that, similarly to the standard Boltzmann picture, isolated KNBH in the microcanonical approach are stable against axisymmetric perturbations in both Tsallis and Rényi models. On the other hand, in considering the case when the black holes are enveloped by a bath of thermal radiation in the canonical treatment, the KNBH based on the Tsallis and Rényi entropies can be stable for some values of the entropy parameters, in contrast to the traditional Boltzmann framework. For the case of Rényi entropy, we find that a Hawking-Page transition and a first order small black hole/large black hole transition can occur in a similar fashion as in rotating black holes in an anti-de Sitter space. Finally, we employ the Ruppeneir geometrothermodynamic technique to provide a new perspective on studying the nature of interactions between black hole microstructures, revealing a non-trivial impact of nonextensive entropies.

Generalized Maxwell equal area law and black holes in complex free energy

Maxwell equal area law is an important and traditional analytical tool in thermodynamic phase transition, especially in the calculation of gas-liquid phase transition, which reconciles the theoretical calculation with the experimental results. Undoubtedly, its importance is also self-evident for the black hole thermodynamic system. In this study, we construct a generalized Maxwell equal area law, which allows different states of thermodynamic systems to be within the generalized free energy. The black hole thermodynamic characteristics are spontaneously emerged in the free energy landscape. Furthermore, by analytic continuation, we utilize the properties of analytical functions to investigate some universal characteristics of thermodynamic phase transitions in black holes, and preliminarily establish the counterpart of thermodynamic phase transitions in the complex domain.

Thermodynamics and Phase Transitions of Dyonic AdS Black Holes in Gauss-Bonnet-Scalar Gravity

In this paper, by treating the cosmological constant as a thermodynamic pressure, we study the thermodynamics and phase transitions of the dyonic AdS black holes in Gauss-Bonnet-Scalar gravity, where the conformal scalar field is considered. In a more general extended phase space, we first verified the first law of black hole thermodynamics, and find that it is always true. Meanwhile, the corresponding Smarr relation is also obtained. Then, we found that this black hole exhibits interesting critical behaviors in six dimensions, i.e., two swallowtails can be observed simultaneously. Interestingly, in a specific parameter space, we observed the small/intermediate/large black hole phase transitions, with the triple point naturally appearing. Additionally, the small/large black hole phase transition, similar to the liquid/gas phase transition of the van der Waals fluids, can also be found in other parameter regions. Moreover, we note that the novel phase structure composed of two separate coexistence curves discovered in the dyonic AdS black holes in Einstein-Born-Infeld gravity disappears in Gauss-Bonnet-Scalar gravity. This suggests that this novel phase structure may be related to gravity theory, and importantly, it is generally observed that the triple point is a universal property of dyonic AdS black holes. On the other hand, we calculated the critical exponents near the critical points and found that they share the same values as in mean field theory. Finally, it is true that these results will provide some deep insights into the interesting thermodynamic properties of the dyonic AdS black holes in the background of conformal scalar fields.

The deep-acceptor nature of the chalcogen vacancies in 2D transition-metal dichalcogenides

Chalcogen vacancies in the semiconducting monolayer transition-metal dichalcogenides (TMDs) have frequently been invoked to explain a wide range of phenomena, including both unintentional p-type and n-type conductivity, as well as sub-band gap defect levels measured via tunneling or optical spectroscopy. These conflicting interpretations of the deep versus shallow nature of the chalcogen vacancies are due in part to shortcomings in prior first-principles calculations of defects in the semiconducting two-dimensional TMDs that have been used to explain experimental observations. Here we report results of hybrid density functional calculations for the chalcogen vacancy in a series of monolayer TMDs, correctly referencing the thermodynamic charge transition levels to the fundamental band gap (as opposed to the optical band gap). We find that the chalcogen vacancies are deep acceptors and cannot lead to n-type or p-type conductivity. Both the (0/−1) and (−1/−2) transition levels occur in the gap, leading to paramagnetic charge states S=1/2 and S = 1, respectively, in a collinear-spin representation. We discuss trends in terms of the band alignments between the TMDs, which can serve as a guide to future experimental studies of vacancy behavior.

View of thermodynamic phase transition of the charged Gauss–Bonnet AdS black hole via the shadow

We examine thermodynamic phase transition (PT) of the charged Gauss–Bonnet AdS black hole (BH) by utilizing the shadow radius. In this system, we rescale the corresponding Gauss–Bonnet coefficient α by a factor of 1/(D–4), and ensure that α is positive to avoid any singularity problems. The equation derived for the shadow radius indicates that it increases as the event horizon radius increases, making it an independent variable for determining BH temperature. By investigating the PT curve in relation to shadows, we can observe that the shadow radius can be used as an alternative to the event horizon radius in explaining the phenomenon of BH PT. Furthermore, the results indicate that an increase in the parameter α corresponds to a decrease in the temperature of the BH. By utilizing the relationship between the temperature and the shadow radius, it is possible to obtain the thermal profile of the Gauss–Bonnet AdS BH. It is evident that there is an N-type variation in temperature for pressures P < P c. Additionally, as the parameter α increases, the region covered by shadow expands while the temperature decreases. The utilization of BH shadows as a probe holds immense significance in gaining a deeper understanding of BH thermodynamic behavior.

Perturbative effective field theory expansions for cosmological phase transitions

Guided by previous non-perturbative lattice simulations of a two-step electroweak phase transition, we reformulate the perturbative analysis of equilibrium thermodynamics for generic cosmological phase transitions in terms of effective field theory (EFT) expansions. Based on thermal scale hierarchies, we argue that the scale of many interesting phase transitions is in-between the soft and ultrasoft energy scales, which have been the focus of studies utilising high-temperature dimensional reduction. The corresponding EFT expansions provide a handle to control the perturbative expansion, and allow us to avoid spurious infrared divergences, imaginary parts, gauge dependence and renormalisation scale dependence that have plagued previous studies. As a direct application, we present a novel approach to two-step electroweak phase transitions, by constructing separate effective descriptions for two consecutive transitions. Our approach provides simple expressions for effective potentials separately in different phases, a numerically inexpensive method to determine thermodynamics, and significantly improves agreement with the non-perturbative lattice simulations.

Monte Carlo study for the thermodynamic and dynamic phase transitions in the spin-S Ising model on Sierpiński carpet

We study the thermodynamic and dynamic phase transitions (TPT and DPT) of the spin- 1/2 and spin-1 Ising models on three graphs constructed on the Sierpiński carpet. This study employs Monte Carlo methods, specifically the Wolff and Metropolis algorithms, in conjunction with finite-size scaling analysis. By calculating the critical temperature and critical exponent ratio γ/ν associated with the TPT, we demonstrate that the three graphs exhibit an identical critical exponent ratio for both the spin- 1/2 and spin-1 Ising models within statistical error. Furthermore, we explore the kinetic Ising model by varying the period of the oscillating external magnetic field and verify the existence of the DPT. We find that the critical exponent ratio γ/ν for the DPT matches that of the TPT. Our results suggest that the critical exponents or their ratios for continuous phase transitions in equilibrium and non-equilibrium systems with short-range interactions are independent of the graph structure and interaction type, as long as the background space is the same.

Thermodynamics of phase transitions in Zintl clusters from density functional theory: making and breaking of bonds in Ba3Ge4.

Density functional theory, in conjunction with the quasi-harmonic approximation, has been used to study the equilibrium between the orthorhombic and tetragonal phases of Ba3Ge4. A transition from the high-temperature tetragonal phase containing isolated Ge46- units to the low-temperature orthorhombic phase, where precisely half of the Ge46- units are polymerised along one axis, is predicted at 930 K, somewhat higher than the experimental value of 630 K. An analysis of the phonon density of states shows that the lower entropy of the orthorhombic phase is not associated directly with the polymerisation of the Ge46- units, but rather with the contraction of the unit cell, which raises the frequencies of ion-ion modes involving the relative motions of the Ba2+ and Ge46- units. Calculations also predict that a third, as yet unobserved, p-tetragonal phase, where all of the Ge46- units are polymerised to form two separate chains running in orthogonal directions, might be accessible at pressures close to 1 GPa.

In situ investigation of controlled polymorphism in mechanochemistry at elevated temperature

Through thermo-mechanochemical conditions it is possible to generate metastable crystal forms below equilibrium thermodynamic transition temperatures, making thermo-mechanical conditions an exciting new direction for solid form control.