Thermodynamic Potential Research Articles

Ultraviolet active novel chalcogenides AScSe2 (A= K, Cs): The structural, optoelectronic, mechanical, vibrational, and thermodynamical properties for energy harvesting applications

It is essential nowadays to investigate some unique and appropriate materials for optoelectronic applications. We deliberate here for the first time, the structural, optoelectronic, mechanical, vibrational, and thermodynamical properties of hexagonal structured selenium-based ternary chalcogenides AScSe2 (A = K, Cs) by using Perdew-Burke-Ernzerhof Generalized-Gradient-Approximation (PBE-GGA). The lattice angles for these materials are found as α = β = 90° and γ = 120°. KScSe2 is optimized with lattice parameters a = b = 4.3 (Å), c = 7.81 (Å) whereas, CsScSe2 is relaxed at a = b = 4.43 (Å) and c = 8.51 (Å). The hybrid Heyd-Scuseria-Ernzerhof (HSE06) functional overestimates the lattice parameters to the extent that for KScSe2 these are found as a = b = 4.92 (Å), c = 7.10 (Å) and for CsScSe2 a = b = 5.15 (Å), c = 7.09 (Å). The energy band gap confirms the semiconducting nature of these materials. Born's criteria endorses the mechanical stability of these materials. Moreover, the temperature dependence of thermodynamic potentials and specific heat at constant volume is also determined using the harmonic approximation. The negative value of free energy ensures their thermodynamical stability. The vibrational modes are calculated by plotting the phonon dispersion and the vibrational density of states (VDOS) where infrared (IR) and Raman spectroscopy are used to characterize the vibrational modes. The optical parameters are examined at a smearing value of 0.5 eV that portray good absorptivity of the incident light from the Ultraviolet (UV) region. Thus, these materials may be potential ones to be utilized for energy harvesting applications via photovoltaic.

Topological susceptibility and axion potential in two-flavor superconductive quark matter

We study the potential of the axion, a, of Quantum Chromodynamics, in the two-flavor color superconducting phase of cold and dense quark matter. We adopt a Nambu-Jona-Lasinio-like model. Our interaction contains two terms, one preserving and one breaking the U(1)A symmetry: the latter is responsible of the coupling of axions to quarks. We introduce two quark condensates, hL and hR, describing condensation for left-handed and right-handed quarks respectively; we then study the loci of the minima of the thermodynamic potential, Ω, in the (hL,hR) plane, noticing how the instanton-induced interaction favors condensation in the scalar channel when the θ angle, θ=a/fa, vanishes. Increasing θ we find a phase transition where the scalar condensate rotates into a pseudoscalar one. We present an analytical result for the topological susceptibility, χ, in the superconductive phase, which stands both at zero and at finite temperature. Finally, we compute the axion mass and its self-coupling. In particular, the axion mass ma is related to the full topological susceptibility via χ=ma2fa2; hence our result for χ gives an analytical result for ma in the superconductive phase of high-density Quantum Chromodynamics. Published by the American Physical Society 2024

Phase transition and central charge criticality of RN AdS black hole immersed in perfect fluid dark matter

This paper delves into the thermodynamic properties of RN AdS black hole immersed in perfect fluid dark matter. We vary the Newton’s gravitational constant, cosmological constant and the perfect fluid dark matter parameter in the bulk. When studying the first law of thermodynamics for black holes, the boundary conformal field theory introduces the central charge, leading to modifications in the thermodynamic volume and chemical potential of black hole. Our analysis shows that the black hole’s free energy is affected by changes in both the central charge and the parameter of perfect fluid dark matter. The F−T curve shows a swallowtail behavior when central charge is above a critical value, which means the occurrence of first-order phase transition from a small black hole to a large black hole. Additionally, we analyzed the heat capacity as a function of temperature for different PFDM parameter values to study the stability of the black hole.

Vanadium oxide clusters in substellar atmospheres. A quantum chemical study

As a refractory material, vanadia (solid V$_2$O$_5$) is likely to be found as a condensate in the atmospheres of substellar objects such as exoplanets and brown dwarfs. However, the nature of the nanometer-sized vanadium oxide clusters that partake in the nucleation process is not well understood. We aim to understand the formation of cloud condensation nuclei in oxygen-rich substellar atmospheres by calculating the relevant fundamental properties of the energetically most favorable vanadium oxide molecules and clusters and, investigate how they contribute to the formation of condensation seeds. We applied a hierarchical optimization approach in order to find the most favourable structures for clusters of (VO) N and (VO$_2$) N for N=1-10, and of (V$_2$O$_5$) N for N=1-4, and to calculate their thermodynamical potentials. The candidate geometries are initially optimized by applying classical interatomic potentials; these are then refined at the B3LYP/cc-pVTZ level of theory to obtain accurate zero-point energies and thermochemical quantities. We present previously unreported vanadium oxide cluster structures as the lowest-energy isomers. Moreover, we report revised cluster energies and their thermochemical properties. Chemical equilibrium calculations are used to asses the impact of the updated and newly derived thermodynamic potentials on the gas-phase abundances of vanadium-bearing species. In chemical equilibrium, larger clusters from different stoichiometric families are found to be the most abundant vanadium-bearing species for temperatures below sim 1000 K, while molecular VO is the most abundant between sim 1000 K and sim 2000 K. We determine the nucleation rates of each stoichiometric family for a given (T$_ gas $, p$_ gas $) profile of a brown dwarf using both classical and non-classical nucleation theory. Small differences in the revised Gibbs free energies of the clusters have a large impact on the abundances of vanadium-bearing species in chemical equilibrium at temperatures below sim 1000 K. These abundance changes subsequently have an impact on the nucleation rates of each stoichiometric family. We find that with the revised and more accurate cluster data, non-classical nucleation rates are up to 15 orders of magnitude higher than classical nucleation rates.

Thermal expansion, [formula omitted] phase diagram and polarization of (1-x)Na[formula omitted]Bi[formula omitted]TiO[formula omitted]-xBaTiO[formula omitted] solid solutions

The paper presents the results of detailed studies of thermal expansion of solid solutions (1-x)Na1/2Bi1/2TiO3-xBaTiO3 with x=0.04-0.97 in the temperature range from 100 to 900 K. A change in chemical pressure associated with the complex cationic substitution, (Na1/2Bi1/2)2+→ Ba2+, result in a very rapid decrease in the temperatures of the transformation P4mm→C2mm→R3m below 100 K which are characteristic of BaTiO3. Significant features in the behavior of thermal expansion were observed near two triple points in the T−x phase diagram where the phases Pm3̄m, P4mm, P4bm (x≈0.15-0.20) and P4bm, P4mm, R3c (x≈0,06) coexist, allow the studied solid solutions to be divided into three groups. The relationship between the effects of internal chemical pressure and external hydrostatic one is discussed. By analyzing the thermodynamic potential, the root-mean-square polarization Pd is determined, which increases by about 16% with a decrease in the BT content from 0.97 to 0.4.

Thermodynamic potential and drag force of the impurity-polariton many-body interaction

Investigating the many-body interaction among polaritons is a fundamental goal in comprehending nonlinear behaviors in microcavity semiconductor systems. Hence, the present study focuses on exploring the many-body interaction between excitons and impurities. It was observed that the energy eigenequation governing this system is of sixth-order, rendering it unsolvable. Consequently, a strategy involving the utilization of impurity weight was employed to partition the initial energy eigenequation into two fourth-order equations, a method deemed suitable for lower order approximations. Subsequently, Green’s function was applied to these two fourth-order equations. The analysis of the computed results, encompassing the energy spectrum, polariton density, and thermodynamic potential of the system, reveals that the many-body interaction between excitons and impurities induces the emergence of novel bound states of quasiparticles. Moreover, the inclusion of impurities leads to a decrease in both energy and density of polaritons. Furthermore, the investigation delves into the drag force exerted by impurities on excitons, demonstrating that the drag force escalates in a second-order fashion with impurity velocity and persists even as impurity velocity increases, surpassing the Landau’s equilibrium theory.

Experimental investigation of a transcritical CO2 refrigeration system incorporating rotary gas pressure exchanger and low lift ejectors

Natural refrigerants like CO2 are playing a significant role in making refrigeration and heat pump systems climate-friendly by slowly phasing out the high global warming refrigerants like hydrofluorocarbons (HFCs). However, the efficiency of a transcritical CO2 refrigeration system declines significantly when the ambient temperature increases, primarily attributed to the high-pressure lift and the losses incurred during expansion. To remedy this issue, this paper presents a novel rotary gas pressure exchanger (PXG) device, which simultaneously achieves high differential pressure expansion work recovery and the “free compression” of the portion of the flash gas in a compact, rotary machine. For this, a PXG device is designed, fabricated, and tested to achieve free compression of CO2 over the entire differential pressure of approximately 70 bar between a receiver and a gas cooler. This is one of the highest free-pressure lift provided by any device to date in CO2 refrigeration. However, there is a small pressure loss of approximately 1–2 bar in the system due to viscous and inertia losses in the piping and in the PXG itself, which needs to be overcome by an external booster device. Results on a baseline PXG integrated system with two low lift booster compressors are presented, which show up to 60 bar free pressure lift and up to 18.2 % COP improvement provided by PXG. Additionally, key performance characteristics of the PXG, like the expansion work recovery, the mass boost ratio, direct fluid-to-fluid contact, and no pass-through operation are experimentally quantified. This work also presents a novel method to integrate two low lift ejectors with PXG to eliminate the need for separate low lift compressors. The low lift ejectors are designed, fabricated, and tested in-house, followed by their integration with the PXG device. A new type of transcritical CO2 refrigeration system is designed to integrate these low lift ejectors with PXG, and experiments are conducted at various evaporator thermal duties and gas cooler exit temperatures, simulating varying ambient temperature conditions. A novel control system to control the gas cooler pressure to optimal thermodynamic levels using PXG rotational speed is demonstrated experimentally. Further, automated control of high-pressure low lift ejector mass flow using an in-built needle design has been successfully demonstrated to optimise PXG mass boost performance. The LP low lift ejector achieved a successful pressure lift of 3.8 bar, and the HP low lift ejector showed a lift of 5.7 bar on the top of 42 bar free pressure lift provided by PXG for up to 5.8 kg/min mass flow delivered by free PXG compression. The results from this study demonstrate that the PXG device provides a significant energy efficiency improvement to the transcritical CO2 refrigeration system, and the novel low lift ejectors, when integrated with PXG, provide a successful method to maximise PXG’s thermodynamic potential.

Surfactant-free CuPd nano-alloy for N2H4 oxidation-assisted H2 evolution and H2O2 detection

The utilization of hydrazine oxidation reaction (HzOR) with a lower thermodynamic oxidation potential has been regarded as an efficient strategy for H2 generation through electrolysis. However, a highly efficient and stable bifunctional electrocatalyst for overall hydrazine (N2H4) splitting was scarce. This work verified promising CuPd nano-alloy as a bifunctional electrocatalys for energy-efficient electrolytic hydrogen production, with hydrazine assistance. It is demonstrated that the CuPd nano-alloy exhibited enhanced electrocatalytic activity for both cathodic and anodic reactions compared to pure Cu and Pd nanocrystals, benefiting from its favorable electronic structure. Under 1.0 M KOH electrolyte with 0.1 M N2H4, the surfactant-free CuPd nano-alloy only required a potential of 0.648 V to achieve the N2H4 splitting (OHzS). The surfactant-free surface maximized exposed active sites, which facilitated the adsorption and desorption of reactants, resulting in enhanced electrocatalytic activity. And working potential for HzOR by surfactant-free CuPd was only 50.4 % compared to the CuPd nano-alloy with surfactant. This work provided an efficient electrocatalyst for OHzS. The enhanced electro-catalytic performances resulting from the electronic structure of alloy and the surfactant-free interface effect have been thoroughly discussed and verified, which would be invaluable for the design of efficient electrocatalysts for H2 production.

Energy‐saving hydrogen production by heteroatom modulations coupling urea electrooxidation

AbstractDeveloping efficient electrocatalysts with low‐cost for the urea oxidation reaction (UOR) is a significant challenge in energy‐saving H2 production owing to its lower thermodynamic potential. Heteroatom incorporation strategy has been proven to boost electrocatalytic activity by altering electronic structures and revealing more active sites on catalysts. Herein, nickel hydroxide nanosheets with various vanadium incorporation (Vx‐Ni(OH)2) were developed through a facile hydrothermal approach. By optimizing the incorporated vanadium contents, V6‐Ni(OH)2 catalyst exhibited easily accessible active sites and enhanced charge transfer with structural advantages, then assembled as the working electrode for urea‐assisted H2 production. Consequently, V6‐Ni(OH)2 catalyst demonstrated superior UOR activity compared with other incorporated samples with an overpotential of 1.33 V and a Tafel slope of 28.3 mV dec−1. Theoretical calculations revealed that the improved UOR activity was attributed to the potential determining step of V‐Ni(OH)2, which exhibited lower energy in comparison with the pristine Ni(OH)2 and increased electronic states density near the Fermi level. Both experimental and theoretical calculations confirmed vanadium incorporation on Ni(OH)2 could modify the electronic structure of Ni(III) species, improving electrical conductivity, and optimizing the adsorption energy for key reaction intermediates. Furthermore, the crucial contribution of vanadium incorporation with optimized electronic structures to the high UOR activity of Ni(OH)2 is demonstrated.image

Unlocking and optimizing the thermodynamic potential of tetragonal Si and Ge: Strategies and insights from a tight-binding simulation framework for material engineering

This study theoretically explores the effects of external fields and doping on the electronic and thermoelectric properties of tetragonal silicon (T-Si) and tetragonal germanium (T-Ge) structures using a tight-binding model, Green’s function formalism, and the Kubo formula. External parameters modify the positions and intensities of the density of states (DOS) peaks, influencing charge carrier excitation and conductivity trends. Applying bias voltage introduces zero-intensity regions in thermal conductivity due to band gap opening, reducing thermal properties. In contrast, chemical potential and magnetic field significantly enhance thermal properties by increasing intensity and shifting the peak position. T-Ge exhibits higher thermal properties than T-Si across the selected parameter ranges. The findings highlight the potential for optimizing and enhancing the thermoelectric properties of tetragonal structures through external controllable parameters.

Classical and quantum thermodynamics described as a system-bath model: The dimensionless minimum work principle.

We formulate a thermodynamic theory applicable to both classical and quantum systems. These systems are depicted as thermodynamic system-bath models capable of handling isothermal, isentropic, thermostatic, and entropic processes. Our approach is based on the use of a dimensionless thermodynamic potential expressed as a function of the intensive and extensive thermodynamic variables. Using the principles of dimensionless minimum work and dimensionless maximum entropy derived from quasi-static changes of external perturbations and temperature, we obtain the Massieu-Planck potentials as entropic potentials and the Helmholtz-Gibbs potentials as free energy. These potentials can be interconverted through time-dependent Legendre transformations. Our results are verified numerically for an anharmonic Brownian system described in phase space using the low-temperature quantum Fokker-Planck equations in the quantum case and the Kramers equation in the classical case, both developed for the thermodynamic system-bath model. Thus, we clarify the conditions for thermodynamics to be valid even for small systems described by Hamiltonians and establish a basis for extending thermodynamics to non-equilibrium conditions.

Covariant phase space analysis of Lanczos-Lovelock gravity with boundaries

This work introduces a novel prescription for the expression of the thermodynamic potentials associated with the couplings of a Lanczos-Lovelock theory. These potentials emerge in theories with multiple couplings, where the ratio between them provide intrinsic length scales that break scale invariance. Our prescription, derived from the covariant phase space formalism, differs from previous approaches by enabling the construction of finite potentials without reference to any background. To do so, we consistently work with finite-size systems with Dirichlet boundary conditions and rigorously take into account boundary and corner terms: including these terms is found to be crucial for relaxing the integrability conditions for phase space quantities that were required in previous works. We apply this prescription to the first law of (extended) thermodynamics for stationary black holes, and derive a version of the Smarr formula that holds for static black holes with arbitrary asymptotic behaviour.

Modified error-in-constitutive-relation (MECR) framework for the characterization of linear viscoelastic solids

We develop an error-in-constitutive-relation (ECR) approach toward the full-field characterization of linear viscoelastic solids described within the framework of standard generalized materials. To this end, we formulate the viscoelastic behavior in terms of the (Helmholtz) free energy potential and a dissipation potential. Assuming the availability of full-field interior kinematic data, the constitutive mismatch between the kinematic quantities (strains and internal thermodynamic variables) and their “stress” counterparts (Cauchy stress tensor and that of thermodynamic tensions), commonly referred to as the ECR functional, is established with the aid of Legendre–Fenchel gap functionals linking the thermodynamic potentials to their energetic conjugates. We then proceed by introducing the modified ECR (MECR) functional as a linear combination between its ECR parent and the kinematic data misfit, computed for a trial set of constitutive parameters. The affiliated stationarity conditions then yield two coupled evolution problems, namely (i) the forward evolution problem for the (trial) displacement field driven by the constitutive mismatch, and (ii) the backward evolution problem for the adjoint field driven by the data mismatch. This allows us to establish compact expressions for the MECR functional and its gradient with respect to the viscoelastic constitutive parameters. For generality, the formulation is established assuming both time-domain (i.e. transient) and frequency-domain data. We illustrate the developments in a two-dimensional setting by pursuing the multi-frequency MECR reconstruction of (i) piecewise-homogeneous standard linear solid, and (b) smoothly-varying Jeffreys viscoelastic material.

High-efficient acetylene synthesis by selective electrochemical formation of CO2-derived CaC2

Acetylene can be used as feedstock for various chemical products, but its raw material has been a fossil fuel, which poses an environmental challenge. One way to address the challenge is to form CaC2 from CO2, which reacts with water to form acetylene. This study demonstrated the selective formation of CaC2 from CO2 by an electrochemical process in NaCl-KCl-CaCl2-CaO melt at 823 K to produce C2H2 with high current efficiency. The CaC2 was formed through two reactions: the carbon electrodeposition from CO2-derived CO32− (Step 1) and the electrochemical reduction of Ca(II) ion on the carbon (Step 2). These two reactions could be controlled by conducting potentiostatic electrolysis under CO2 and Ar atmospheres, resulting in acetylene synthesis with a maximum current efficiency of 92 %. Each electrochemical reaction agreed with the thermodynamic electrode potential. The electrolysis on carbon electrodes revealed that the higher the crystallinity of carbon, the more selectively CaC2 was formed. The CaC2 formation was induced by the reduction of Ca(II) ions on the basal plane of the graphite layer rather than the edge plane. The unique interfacial phenomenon between high-temperature melt and a carbon electrode surface will contribute to realizing a highly efficient CO2 conversion process to acetylene.

Topology of thermodynamic potentials using physical models: Helmholtz, Gibbs, Grand, and Null.

Thermodynamic potentials play a substantial role in numerous scientific disciplines and serve as basic constructs for describing the behavior of matter. Despite their significance, comprehensive investigations of their topological characteristics and their connections to molecular interactions have eluded exploration due to experimental inaccessibility issues. This study addresses this gap by analyzing the topology of the Helmholtz energy, Gibbs energy, Grand potential, and Null potential that are associated with different isothermal boundary conditions. By employing Monte Carlo simulations in the NVT, NpT, and μVT ensembles and a molecular-based equation of state, methane, ethane, nitrogen, and methanol are investigated over a broad range of thermodynamic conditions. The predictions from the two independent methods are overall in very good agreement. Although distinct quantitative differences among the fluids are observed, the overall topology of the individual thermodynamic potentials remains unaffected by the molecular architecture, which is in line with the corresponding states principle-as expected. Furthermore, a comparative analysis reveals significant differences between the total potentials and their residual contributions.

Semiclassical thermodynamic geometry.

In this work the thermodynamic geometry (TG) of semiclassical fluids is analyzed. We present results for two models. The first one is a semiclassical hard-sphere (SCHS) fluid whose Helmholtz free energy is obtained from path-integral Monte Carlo simulations. It is found that, due to quantum contributions in the thermodynamic potential, the anomaly found in TG for the classical hard-sphere fluid related to the sign of the scalar curvature is now avoided in a considerable region of the thermodynamic space. The second model is a semiclassical square-well fluid, described by a SCHS repulsive interaction coupled with a classical attractive square-well contribution. The behavior of the semiclassical curvature scalar as a function of the thermal de Broglie wavelength λ_{B} is analyzed for several attractive-potential ranges. A description of the semiclassical R Widom lines, defined by the maxima of the curvature scalar, is also obtained and results are compared with the corresponding classical systems for different square-well ranges.

On the state principle of classical thermodynamics

We discuss the state principle of classical thermodynamics, namely that the thermodynamic state of a simple compressible system can be uniquely determined by specifying two independent properties. We show that for certain combinations of properties, one is not guaranteed to arrive at a unique state. This caveat to the state principle is illustrated with three examples, two involving liquid water and a third using real gases. Finally, we show that to guarantee a unique state for a simple compressible system, the required two independent properties must be chosen from the trio consisting of a thermodynamic potential and its two natural variables.

Design, Multi-Point Optimization, and Analysis of Diffusive Stator Vanes to Enable Turbine Integration Into Rotating Detonation Engines

Abstract Pressure gain combustion is considered a possible path toward improved thermal cycle efficiency and reduced carbon emissions. However, ad hoc turbine designs are required to maximize the thermodynamic potential; the new turbomachinery should be suited for the oscillations in flow conditions generated by the detonation combustor, which are very different from conventional gas turbines. This paper investigates the design, optimization, and analysis of diffusive stator vanes operating under large inlet flow angles in the high-subsonic regime. First, the design methodology is outlined, focusing on the geometric requirements to ingest high Mach number flow and the parametric modeling of the endwall and the 3D vane pressure and suction sides. Then, the impact of the inlet flow angle on the flow field and vane design is studied through a multi-point, multi-objective optimization with three different inlet angles, performed using steady Reynolds-averaged Navier–Stokes simulations. Remarkable reductions in pressure loss and stator-induced rotor forcing are attained while maintaining an extensive operating envelope and high flow turning. Moreover, several design guidelines are provided based on the analysis of the optimized geometries. Finally, the effectiveness of the proposed methodology is verified with an unsteady assessment of the baseline and optimized vane designs.

Refining Combustion Dynamics: Dissolved Hydrogen in Diesel Fuel within Turbulent-Flow Environments

This article presents the possibility of improving combustion using the effect of releasing hydrogen from a solution with nucleation of gas bubbles. This concept consists in dissolving hydrogen in diesel fuel until the equilibrium state of the solution is reached. At a later stage, the phenomenon is reversed, and this gas is released from the solution during its injection into the combustion chamber with a strong swirl. A characteristic feature of the solution is that when lowering the pressure (opening the atomizers), there is a decrease in the equilibrium thermodynamic potential, which results in the excess, dissolved hydrogen being released spontaneously, and this process is of a volumetric nature. This article is a continuation of the work carried out at Poznan University of Technology on the development of this concept. This article presents the results of tests for the impact of hydrogen dissolved in diesel fuel on the combustion process within a turbulent-flow environment. The tests were conducted in the combustion chamber of an engine equipped with a toroidal combustion chamber and direct injection. During the tests, the following factors were measured: the main indicators of motor operation, emission of hydrocarbons, carbon monoxide, nitrogen oxides, and particulate matters.

Topological interpretation of extremal and Davies-type phase transitions of black holes

Topological arguments are currently being used as a novel scheme to discern the properties of black holes while ignoring their detailed structure and specific field equations. Among various avenues of black hole physics, where this novel approach is being utilized, the phase transition in black hole thermodynamics lies at the forefront. There are several types of phase transition in black holes; such as the van der Waals type phase transition, Davies-type phase transition, extremal phase transition, and Hawking-Page (HP) transition. So far, the topological interpretation, where the critical point has been identified with the non-zero topological charge, has been obtained only for the van der Waals type phase transition and HP transition in different spacetimes. To complete the picture, here we provide the same interpretation for two other phase transitions: Davies-type phase transition and extremal phase transition. The entire analysis is general and is valid for any spacetime where these types of phase transitions are observed. More importantly, our analysis suggests that amid the apparent differences in these phase transitions, they share the same topological characteristics, i.e. non-zero topological charge arising from different thermodynamic potentials in different types of phase transition.