Terms Of Chemical Potential Research Articles

Entanglement Hamiltonian in the non-Hermitian SSH model

Entanglement Hamiltonians provide the most comprehensive characterisation of entanglement in extended quantum systems. A key result in unitary quantum field theories is the Bisognano-Wichmann theorem, which establishes the locality of the entanglement Hamiltonian. In this work, our focus is on the non-Hermitian Su-Schrieffer-Heeger (SSH) chain. We study the entanglement Hamiltonian both in a gapped phase and at criticality. In the gapped phase we find that the lattice entanglement Hamiltonian is compatible with a lattice Bisognano-Wichmann result, with an entanglement temperature linear in the lattice index. At the critical point, we identify a new imaginary chemical potential term absent in unitary models. This operator is responsible for the negative entanglement entropy observed in the non-Hermitian SSH chain at criticality.

Exploring the Manufacturing Process of a Renaissance Breach Pike

An archaeometallurgical study of a Renaissance breach pike was performed to elucidate its manufacturing process. Optical microscopy observations and microhardness measurements indicated that the breach pike was forged starting from a heterogeneous steel lump. The microstructural features were compatible with post-forging air cooling. The chemistry of a large set of nonmetallic inclusions was investigated by scanning electron microscopy coupled with X-ray dispersive spectroscopy. Compositional data were analyzed by multivariate statistics to distinguish smelting-related slag inclusions. A logistic regression model indicated that the steel was probably produced by the direct method. The liquidus temperatures of the slag inclusions indicated maximum smelting temperatures in the range of 1200 °C to 1300 °C. A thermodynamic-based model was adopted to estimate the average smelting conditions in terms of temperature and oxygen chemical potential and investigate the disequilibrium of slag inclusion–metal systems. For low-disequilibrium systems, the computed temperature values range between 1095 °C and 1118 °C, while the oxygen chemical potentials (μO2) span from −442 to −374 kJ/mol.

Archaeometallurgical Characterization of Two Lombard Early Medieval Bloomery Slags from Ponte di Val Gabbia I Site (Northern Italy)

An archaeometallurgical characterization of two iron smelting tap slags recovered from the early medieval site of Ponte di Val Gabbia I (Brescia, northern Italy) was performed. The main goal was to infer from the slags the working conditions of the ancient bloomery furnace in terms of temperature and oxygen chemical potential. The petrology of both slags was investigated by light optical microscopy and scanning electron microscopy, while their chemical compositions were measured via scanning electron microscopy coupled with X-ray dispersive spectroscopy. High-resolution Raman micro-spectrometry was used to confirm the identification of the mineralogical phases. The software Rhyolite-MELTS was used to compute the liquidus temperatures of the two slags, which were found to be 1120 °C and 1146 °C. These temperatures approximate the working temperature of the bloomery furnace. A thermodynamic-based approach was adopted to estimate the redox conditions of the reducing atmosphere of the smelting furnace, revealing that the two slags formed in different redox environments. Specifically, the resulting oxygen chemical potentials were −382.61 kJ/mol and −243.80 kJ/mol at the liquidus temperatures of 1120 °C and 1146 °C, respectively.

Energy dissipative and positivity preserving schemes for large-convection ion transport with steric and solvation effects

Ion transport plays a crucial role in biophysical and electrochemical applications. While being modeled by the classical Poisson–Nernst–Planck (PNP) equations, many ionic features are ignored in the course-graining modeling of ionic interactions. In this work, we study ion transport by modified PNP equations including effects arising from steric interactions and the Born solvation, which both could cause strong convection. The modified NP equations are first rewritten in a gradient-flow reformulation that involves mobility and chemical potential terms. The mobility is then approximated by upwind fluxes with various flux limiters on the half-grid points, and the chemical potential terms are then implicitly approximated by central differencing. The resulting first-order in time scheme is proved to be energy dissipative unconditionally. Furthermore, the unconditional existence of positive numerical concentration is proved by making use of the singularity of the entropy term, which prevents the concentration from approaching zero. The flux with the Minmod or Osher limiter is reduced to a second-order upwind flux in the strong convective limit. Numerical tests are performed to confirm the expected order of accuracy and the properties of the developed scheme at discrete level. In addition, our numerical experiments demonstrate that the developed schemes with limiters can achieve higher accuracy than the Scharfetter-Gummel scheme and classical upwind scheme in tests with strong convection. Finally, the developed schemes are applied to numerically assess the effects of Coulombic interaction, steric interaction, and Born solvation on the rectifying transport of ions through nanopores.

Analysis of Ancient Slag Inclusion-Metal Systems as a Method to Disclose Processing Thermo-chemical Parameters: The Case Study of a Medieval Lombard Steel Bar from Northern Italy

An archaeometallurgical characterization of a VI to VII century Lombard steel bar from Ponte di Val Gabbia I site (northern Italy) was performed to reconstruct its manufacturing process and extract processing thermochemical parameters (i.e., temperature and oxygen chemical potential) from the slag inclusion-metal systems. Metallographic observations by optical microscopy and Vickers microhardness measurements indicated that the steel bar was forged from a heterogeneous steel lump, most probably an iron bloom, which was cooled in the air after the forging process. The chemical composition of non-metallic inclusions was determined by scanning electron microscopy coupled with X-ray dispersive spectroscopy. A multivariate statistical analysis of the smelting-derived non-metallic inclusions chemistry allowed to conclude that the steel bar was obtained by the direct or bloomery method. Under the hypothesis of local near-equilibrium conditions for the slag inclusion-metal systems, a thermodynamic-based strategy was adopted to estimate the firing conditions in the bloomery furnace in terms of both temperature and oxygen chemical potential of the reducing gas atmosphere. In particular, the computed temperatures are in the range of 1003 °C to 1171 °C, whereas the values of oxygen chemical potential vary between − 447.47 and − 385.79 kJ/mol.

Kinetic Relevance of Surface Reactions and Lattice Diffusion in the Dynamics of Ce–Zr Oxides Reduction–Oxidation Cycles

Reduction–oxidation cycles in oxides are ubiquitous in oxygen storage and transport, chemical looping processes, and fuel cells. O-atom addition and removal are mediated by coupling reactions of oxidants and reductants at surfaces with diffusion of O-atoms within oxide crystals, with either or both processes as limiting steps. CeO2–ZrO2 solid solutions (CZO) are ubiquitous in practice. They are used here to illustrate general experimental strategies and reaction–diffusion formalisms for nonideal systems that enable assessments of the kinetic relevance of the steps that mediate O-atom addition and removal in these materials; these experiments are described within the context of models that describe the driving forces for reaction and diffusion rigorously in terms of oxygen chemical potentials (μO). These strategies assess the rate consequences of varying the fluid phase redox potential, through changes in the identity and pressures of the reactants and products used in redox cycles (O2; CO/CO2; H2/H2O; N2O/N2), of introducing dispersed metal nanoparticles that capture and react lattice O-atoms in CZO using CO or H2, and of imposing intervening dwells without reaction within redox cycles. O-removal rates depend on reductant pressures, even when CO/CO2 and H2/H2O ratios are chosen to maintain the same surface μO if surface reactions were quasi-equilibrated. These data, taken together with significant rate enhancements in O-removal when Pt nanoparticles are present at CZO crystal surfaces and with similar rates before and after inert dwells, demonstrate that reduction rates by both CO and H2 are limited by surface reactions without the presence of consequential spatial gradients in μO within CZO crystals. In contrast, O-addition rates to partially reduced CZO crystals are similar for N2O and O2 reactants and are not affected by the presence of Pt nanoparticles; O-addition rates are significantly higher after intervening inert dwells during CZO oxidation, indicative of spatial gradients in μO, which relax during nonreactive periods. These methods and models, illustrated here for CZO redox cycles at conditions relevant to oxygen storage practice, allow systematic assessments of the kinetic relevance of lattice diffusion and surface reactions for systems that use solids for the reversible storage and release of atoms, irrespective of the identity of the solids or the atoms (e.g., O, H, N, and S).

A Comparative Study of Chamomile Essential Oils and Lipophilic Extracts Obtained by Conventional and Greener Extraction Techniques: Chemometric Approach to Chemical Composition and Biological Activity

Bearing in mind the centuries-old traditional use of chamomile, but also the increasing demand for its products in modern industry, oriented toward sustainable development, there are increasing efforts for the efficient extraction of high-value compounds of this plant, as well as obtaining its products with added value. With that goal, conventional and contemporary separation techniques were applied in this work. Both hydrodistillation processes (HD), conducted in a traditional manner and coupled with microwave irradiation (MWHD), were used for essential oil isolation. In parallel with those procedures, chamomile lipophilic extracts were obtained by Soxhlet extraction applying organic solvents and using supercritical fluid extraction as a greener approach. The obtained extracts and essential oils were characterized in terms of chemical composition (GC analysis, contents of total phenolics and flavonoids) and biological potential. GC analysis revealed that oxygenated sesquiterpenes and non-terpene compounds were the dominant compounds. α-Bisabolol oxide A (29.71–34.41%) and α-bisabolol oxide B (21.06–25.83%) were the most abundant individual components in samples obtained by distillation while in supercritical and Soxhlet extracts, major compounds were α-bisabolol oxide A and pentacosane. The biological potential of essential oils and extracts was tested by applying a set of analyzes to estimate the inhibition of biologically important enzymes (amylase, glucosidase, acetylcholinesterase, butyrylcholinesterase, tyrosinase) and antioxidant capacity (DPPH, ABTS, CUPRAC, FRAP, chelating and total antioxidant capacity). The results suggested essential oils as better antioxidants, while the extracts were proven to be better inhibitors of the tested enzymes. Principal Component Analysis was conducted using the experimental results of the composition of extracts and EOs of chamomile obtained by different separation techniques, showing clear discrimination between methods applied in correlation with the chemical profile. Molecular docking was applied for the identification of the main active principles present in the essential oil, among which α-bisabolol-oxide B (cp3) showed a higher affinity for tyrosinase.

The factors of alloying elements on corrosion resistance of aluminum alloys

Corrosion resistance is a key property for aluminum alloys used in automotive heat exchangers. This study focuses on comparing two variations of post-brazed 3003-H24 aluminum alloys with 2-sided cladding 4045. One of them is the special developed for corrosion resistance. Another one is the generic and widely commercial used alloy. The specimens were prepared by heating in the brazing furnace at temperature of 600 °C for 5 min in order to let the clad material diffuse into the core layer to create the corrosion protection layer. This study compared the corrosion resistance of two alloys by the car maker’s Cyclic Condenser Corrosion test method (CCCT). The results indicate that the special developed alloy has better corrosion resistance than the generic alloy. According to the corrosion test result, further study was performed in order to explain potential factors that make the difference between two alloys. The results were discussed in terms of chemical composition, mechanical properties, microstructure and corrosion potential. It was observed that the difference of Fe content in the core layer of the alloys yields highly impact on the corrosion resistance.

Corrections to AdS5 black hole thermodynamics from higher-derivative supergravity

We study four-derivative corrections to five-dimensional minimal gauged supergravity. We evaluate the on-shell action of the AdS5 black hole solution with two independent angular momenta and one electric charge at linear order in the corrections. After imposing supersymmetry, we are able to recast the action in terms of the supersymmetric chemical potentials and match the result obtained from the dual superconformal index on the second sheet. To achieve this, we exploit the freedom to implement field redefinitions to recast the action in a much simpler form, as well as the fact that the two-derivative solution is enough. We use the on-shell action to determine the corrections to the black hole thermodynamics, including those to the entropy and the charges. We then specialize to the supersymmetric and extremal case and find a simple expression for the microcanonical entropy. In particular, for the case with one independent angular momentum the corrections are entirely encoded in the dual superconformal anomaly coefficients. We corroborate this result for the entropy by constructing the corrected near-horizon solution and applying Wald’s formula.

Origins of p-Doping and Nonradiative Recombination in CsSnI3.

It is commonly believed that the spontaneous p-doping in Sn-based perovskites is caused by Sn vacancies. By performing rigorous first-principles calculations for a prototypical Sn-based perovskite CsSnI3 , we reveal that, in fact, the defects dominating p-doping are Cs vacancies. The reason that adding extra Sn2+ could reduce p-doping is that Cs and Sn present the same changing trend in terms of chemical potentials, and thus inhibiting the formation of Sn vacancies will also limit the formation of Cs vacancies. Moreover, we show that I vacancies are the dominant nonradiative recombination centers, and can result in sizable nonradiative losses, which explains why the experimentally measured carrier lifetime is only a few nanoseconds even if p-doping is suppressed. This work provides new insights into the origins of p-doping and nonradiative recombination in CsSnI3 , and suggests that minimizing the formation of Cs and I vacancies is critical to realizing the best device performance.

Origins of p‐Doping and Nonradiative Recombination in CsSnI3

AbstractIt is commonly believed that the spontaneous p‐doping in Sn‐based perovskites is caused by Sn vacancies. By performing rigorous first‐principles calculations for a prototypical Sn‐based perovskite CsSnI3, we reveal that, in fact, the defects dominating p‐doping are Cs vacancies. The reason that adding extra Sn2+ could reduce p‐doping is that Cs and Sn present the same changing trend in terms of chemical potentials, and thus inhibiting the formation of Sn vacancies will also limit the formation of Cs vacancies. Moreover, we show that I vacancies are the dominant nonradiative recombination centers, and can result in sizable nonradiative losses, which explains why the experimentally measured carrier lifetime is only a few nanoseconds even if p‐doping is suppressed. This work provides new insights into the origins of p‐doping and nonradiative recombination in CsSnI3, and suggests that minimizing the formation of Cs and I vacancies is critical to realizing the best device performance.

The open Haldane–Shastry chain: thermodynamics and criticality

We study the thermodynamics and criticality of the su(m|n) Haldane–Shastry chain of BC N type with a general chemical potential term. We first derive a complete description of the spectrum of this model in terms of BC N -type motifs, from which we deduce a representation for the partition function as the trace of a product of site-dependent transfer matrices. In the thermodynamic limit, this formula yields a simple expression for the free energy per spin in terms of the Perron–Frobenius eigenvalue of the continuum limit of the transfer matrix. Evaluating this eigenvalue we obtain closed-form expressions for the thermodynamic functions of the chains with m, n ⩽ 2. Using the motif-based description of the spectrum derived here, we study in detail the ground state of these models and their low energy excitations. In this way we identify the critical intervals in chemical potential space and compute their corresponding Fermi velocities. By contrast with previously studied models of this type, we find in some cases two types of low energy excitations with linear energy-quasimomentum relation. Finally, we determine the central charge of all the critical phases by analyzing the low-temperature behavior of the expression for the free energy per spin.

Verification of stability and unraveling the electronic and physical properties of bulk and (001)-surfaces of newly synthesized Ti2ZnX (X = C, N) MAX phases

MAX phase family has been extended by the addition of late transition metals at the A-site with the expectation of diverse functional properties. Here, we present our systematic density functional investigation on the thermodynamic and phonon stabilities, elastic properties, including elastic constants, elastic moduli and elastic anisotropy of newly synthesized Ti2ZnX (X = C, N) phases in comparison with conventional Ti2AlX (X = C, N). Due to the smaller size of N as compared to C, the unit cell dimension is reduced when C atoms are replaced by N atoms at the X-site. The Ti2ZnC and Ti2ZnN are stable at the equilibrium volume of 110.84 Å3 and 105.70 Å3. The thermodynamic, mechanical and dynamical stabilities are validated by estimating the formation energies, elastic constants and phonon dispersions, respectively. The elastic properties of Ti2ZnN are less anisotropic as compared to those of Ti2ZnC. To understand the thin-film characteristics in Ti2ZnX, the surface properties with (001)-terminated slabs are investigated. Both Ti2ZnX bulk and (001)-surfaces exhibit metal-like electronic structures. There is a strong covalent bonding between Ti-X and Ti-Zn atoms confirmed by the charge density map and Mulliken population analysis. Additional states are generated at the Fermi level (EF) due to the unusual d-p states hybridization between Ti and Zn atoms. The anisotropy in chemical bonding is confirmed by the cleavage energy difference between Ti-X and Ti-Zn. Here, Ti(X)-001 and Zn-001 terminations are stable surfaces; however, in terms of chemical potentials, Zn-001 termination is the most favourable in Ti2ZnX.

The Role of Energy Scales for the Structure of Ionic Liquids at Electrified Interfaces: A Theory-Based Approach.

Ionic liquids offer unique bulk and interfacial characteristics as battery electrolytes. Our continuum approach naturally describes the electrolyte on a macroscale. An integral formulation for the molecular repulsion, which can be quantitatively determined by both experimental and theoretical methods, models the electrolyte on the nanoscale. In this article, we perform a systematic series expansion of this integral formulation, derive a description of chemical potentials in terms of higher-order concentration gradients, and rationalize the appearance of fourth-order derivative operators in modified Poisson equations, as recently proposed in this context. In this way, we formulate a rigorous multiscale methodology from atomistic quantum chemistry calculations to phenomenological continuum models. We apply our generalized framework to ionic liquids near electrified interfaces and perform analytical asymptotic analysis. Three energy scales describing electrostatic forces between ions, molecular repulsion, and thermal motion determine the shape and width of the long-ranging charged double layer. We classify the charge screening mechanisms dependent on the system parameters as dielectricity, ion size, interaction strength, and temperature. We find that the charge density of electrochemical double layers in ionic liquids either decays exponentially, for negligible molecular repulsion, or oscillates continuously. Charge ordering across several ion diameters occurs if the repulsion between molecules is comparable with thermal energy and Coulomb interactions. Eventually, phase separation of the bulk electrolyte into ionic layers emerges once the molecular repulsion becomes dominant. Our framework predicts the exact phase boundaries among these three phases as a function of temperature, dielectricity, and ion size.

Astrophysical chiral dynamos and strain-torsioned Weyl materials

Our goal in this paper is two-fold: First we show that in the absence of four-fermion interactions, from Einstein–Cartan–Maxwell (ECM) anisotropy cosmology, one may derive instabilities in chiral dynamo equations from magnetic perturbations. They are obtained from a model, where the spinning-fluid does not couple directly to the Einstein–Maxwell model. Instead spin fluid enter into the evolution equation of density perturbations. Chiral dynamo equation is obtained from magnetic perturbations in the particular case where the perturbations in the chiral magnetized plasma can be neglected in second order of perturbations. The vanishing of the Nieh–Yan (NY) topological density in this Bianchi type-I model is also investigated. In the second example, use of the magnetic and torsion perturbations are given by the technique of encoding the magnetic perturbations in the metric constrained by teleparallelism. We consider non-uniform chiral chemical potential in the chiral flipping equation in order to obtain the magnetic field dynamo amplification. Dynamo effects are obtained from current perturbations expressed in terms of chiral chemical potential when number density of left-handed chiral particles is approximately zero. The damping found in magnetic field by the end of inflation, may help to explain why so weak galactic dynamo seeds are found at present universe. Furthermore, damping depends upon the strain–torsion relation of the Weyl topological materials. Though in general, torsion does not couple to electromagnetic fields, it influences the magnetic field through strain–torsion pseudo-magnetic potential.

A time–energy uncertainty relation in chemical thermodynamics

An analogy between the thermodynamic inequalities presented by Nicholson et al. [Nat. Phys. 16, 1211 (2020)] and by Yoshimura and Ito [Phys. Rev. Res. 3, 013175 (2021)] is discussed. As a result, a time–energy uncertainty relation in chemical thermodynamics in terms of Gibbs free energy and chemical potential is derived. It is numerically demonstrated that the uncertainly relation holds in a model system of oscillatory Brusselator reactions. Our result bridges the thermodynamic time–information uncertainty relation and free energy evolution in chemical reactions.

Study of vacancy ordered double perovskites In2PtX6 (X = Cl, Br, I) for solar cells and renewable energy, alternative of hybrid perovskites

The electronic, thermoelectric, and optical behavior of vacancy-ordered double perovskites In2PtX6 (X ​= ​Cl, Br, I) have been addressed using density functional theory for energy applications. The tolerance factor has been computed for structural stability, formation energy for thermal stability, and phonon dispersion for dynamic stability. The band structures ensure the band gaps of 2.0 ​eV, 1.96 ​eV, and 1.30 ​eV for In2PtCl6, In2PtBr6, and In2PtI6, respectively. The absorption of light energy is maximum in the ultraviolet region for In2PtCl6 and in the visible region for In2PtBr6 and In2PtI6. Moreover, light reflection and optical energy loss had also been computed. Thermoelectric behavior has been calculated by conductivities and Seebeck coefficient in terms of chemical potential and temperature. The figure of merit ranging from 0.80 to 1.0 in low temperature to room temperature emphasises their importance for thermoelectric applications. The elastic constants confirm mechanical stability and ductile nature. The high melting temperature, hardness, and ultralow lattice thermal conductivity increase the potential of study for device fabrication.

First-principles study of lead-free double perovskites Ga2PdX6 (X = Cl, Br, and I) for solar cells and renewable energy

The double perovskites are promising for solar cells and other optoelectronic applications. In this article, the optoelectronic, transport characteristics of new double perovskites Ga2PdCl6, Ga2PdBr6, and Ga2PdI6 are addressed. The structural and thermodynamic stabilities have been addressed by tolerance factor, and positive frequency of phonon dispersion. The reported band gaps are 2.05 eV, 1.60 eV and 0.80 eV which increases their performance for solar cells. The Ga2PdBr6 is ideal for visible light solar cells with absorption band 400 nm–620 nm. The optical properties analyzed by dielectric constants, polarization, absorption of light, and optical losses. Thermoelectric characteristics has been explained by figure of merit (ZT) in terms of chemical potential, and kelvin temperature. The room temperature ZT (0.77, 0.76, 0.75) for Ga2PdX6 (X = Cl, Br, I) make them potential for thermoelectric applications.

Propagation of phase-imprinted solitons from superfluid core to Mott-insulator shell and superfluid shell

We study phase-imprinted solitons of ultracold bosons in an optical lattice with a harmonic trap, which shows the superfluid (SF) and Mott-insulator (MI) shell structures. The earlier study [Konstantin V. Krutitsky, J. Larson, and M. Lewenstein, Phys. Rev. A 82, 033618 (2010).] reported three types of phase-imprinted solitons in the Bose-Hubbard model: in-phase soliton, out-of-phase soliton, and wavelet. In this paper, we uncover the dynamical phase diagram of these phase-imprinted solitons, and find another type of the phase-imprinted soliton namely, the hybrid soliton. In the harmonically trapped system, the solitonic excitations created at the SF core cannot penetrate into the outer SF shell. This repulsion at the surface of the outer SF shell can be cured by inposing a repulsive potential at the center of the trap. These results can be interpreted as a kind of the impedance matching of excitations in BECs in terms of the effective chemical potentials or the local particle numbers in the shell, and the analogous results can be observed also in the sound wave created by the local single-shot pulse potential.

Proposing ab initio assisted lattice distortion theory for phase equilibrium: Pure and mixed refrigerant gas hydrates

AbstractWith promising applications in cold storage and seawater desalination, various refrigerant gas hydrates are experimentally studied for their phase equilibrium behavior; however, the theoretical modeling to predict their formation conditions is under development. Although a high degree of lattice distortion is expected in these gas hydrates due to highly polar and nonspherical molecules of refrigerants, this issue is not addressed in the van der Waals–Platteeuw theory. With this research gap, we formulate a lattice distortion theory for both pure and mixed refrigerant hydrates. For the first time, ab initio methodology comprising the spin‐component scaled MP2 method with Dunning's basis set is implemented for estimating cavity potential of refrigerant hydrates. The extent of lattice distortion is documented in terms of reference chemical potential and enthalpy differences, which are obtained by regressing the Holder's equation with the experimental data of refrigerant hydrate formation. A critical observation is made that the reference properties linearly vary with the “Boltzmann weighted energy‐well depth” of the guest. Analyzing the accuracy of the model using average absolute relative deviation between experimental and predicted pressure of hydrate formation, the proposed lattice distortion model outperforms the existing thermodynamic models for variety of pure and mixed refrigerant hydrates.