Electronic Heat Capacity Research Articles

First principles investigation of structural, elastic, thermoelectric, electronic and optical properties XH3 (X=Ac, La) for hydrogen storage

Efficient hydrogen storage is essential for its use as an energy source. Considering the various methods, hydrogen storage in solid materials shows great promise but requires further research. This study employs density functional theory using the Wien2k, with the LSDA method to determine the stability of this storage mode, and LSDA + mBJ to calculate the electronic, optical, and thermoelectric properties of AcH3 and LaH3. The electronic properties reveal that XH3 (X = Ac, La) exhibits a semiconducting nature with indirect energy gaps in both cases. The analysis of hydrogen storage properties determined the gravimetric hydrogen storage capacities for AcH3 and LaH3 to be 1.297 and 2.086 wt%, respectively. Calculations of the elastic constants validated the mechanical stability of these compounds. Thermoelectric characteristics, including electrical and thermal conductivity, Seebeck coefficient, electronic specific heat capacity, and Pauli magnetic susceptibility, have been evaluated, highlighting their p-type characteristics. The figure of merit indicates their potential for thermoelectric devices. Gravimetric ratios suggest significant hydrogen storage capacity, which could contribute to various transportation and energy applications.

Charge transport in two-dimensional system with massless Mexican-hat-like bands

We study the single-particle, DC and optical properties of a two-dimensional (2D) system with massless Mexican-hat-like (W-shaped) valence bands. A proposed 2 × 2 Hamiltonian matrix gives the W-bands and two ground state phases: a gapped phase and a nodal-loop phase. The intraband properties include the single particle density of states, the effective concentration of charge carriers (the Drude weight), the Hall coefficient and electron mobility, electronic heat capacity and thermopower. The real part of the interband conductivity is calculated for the gapped phase as it depends on doping and temperature. As for the undoped nodal-loop phase only the zero-frequency interband conductivity is finite. Among several results two most decisively stand out: By measuring the Hall coefficient as a function of doping at zero-temperature we can answer whether the bands are W-shaped. By measuring the square-root singularity in the finite-temperature optical conductivity, we identify the gapped phase.

Nonequilibrium electronic properties and stability consequences in metallic crystalline binary alloys under ultrafast laser excitation

This study undertakes an exhaustive exploration of properties under electron-phonon nonequilibrium for a series of ten industrially pertinent crystalline alloys, namely AlCu, AlNi, AlTi, AuCu, CuNi, CuTi, NbZr, NiTi, NiZr, and ZrCu. This comprehensive investigation encompasses electronic heat capacity, electron-phonon coupling factor, excited electron density, electronic pressure, dielectric function, refractive index, extinction coefficient, reflectivity, and optical penetration depth. Employing ab initio simulations, we meticulously analyze the nonequilibrium optoelectronic attributes inherent to these alloys change under electronic excitation across the temperature range going from 0 to 50,000 K. Additionally, to contextualize the findings, we employ classical Molecular Dynamics coupled with a Two Temperature Model simulation, notably to deliver a deep comprehension of the intricate mechanisms of the CuTi alloy ablation induced by femtosecond laser irradiation.

Infrared single-photon detection with superconducting magic-angle twisted bilayer graphene.

The moiré superconductor magic-angle twisted bilayer graphene (MATBG) shows exceptional properties, with an electron (hole) ensemble of only ~1011 carriers per square centimeter, which is five orders of magnitude lower than traditional superconductors (SCs). This results in an ultralow electronic heat capacity and a large kinetic inductance of this truly two-dimensional SC, providing record-breaking parameters for quantum sensing applications, specifically thermal sensing and single-photon detection. To fully exploit these unique superconducting properties for quantum sensing, here, we demonstrate a proof-of-principle experiment to detect single near-infrared photons by voltage biasing an MATBG device near its superconducting phase transition. We observe complete destruction of the SC state upon absorption of a single infrared photon even in a 16-square micrometer device, showcasing exceptional sensitivity. Our work offers insights into the MATBG-photon interaction and demonstrates pathways to use moiré superconductors as an exciting platform for revolutionary quantum devices and sensors.

Drude’s lesser known error of a factor of two and Lorentz’s correction

As is well known, Paul Drude put forward the very first quantitative theory of electrical conduction in metals in 1900. He could successfully account for the Wiedemann–Franz law which states that the ratio of thermal to electrical conductivity divided by temperature is a constant called the Lorenz number. As it turns out, in Drude’s derivation there is a lucky cancellation of two errors. Drude’s underestimatation (by an order of 100) of the value of square of the average electron velocity compensated for his overestimatation of the electronic heat capacity (by the same order of 100). This compensation or cancellation of two errors lead to a value of the Lorenz number very close to its experimental value; which is well known. There is another error of a factor of two which Drude made when he calculated two different relaxation times for heat conductivity and electrical conductivity; in this article we highlight how and why this error occurred in Drude’s derivation and how it was removed 5 years later (in 1905) by Hendrik Lorentz when he used the Boltzmann equation and a single relaxation time. This article is of pedagogical value and may be useful to undergraduate/graduate students learning solid state physics.

Exploration of a New α-T3 System for Electronic Heat Capacity and Pauli Magnetic Susceptibility Properties via the Kane-Mele and Hubbard Model

Exploration of a New α-T₃ System for Electronic Heat Capacity and Pauli Magnetic Susceptibility Properties via the Kane-Mele and Hubbard Model

Study of magnetic, thermodynamic and transport properties of Laves phase NdRh[formula omitted]

The results of magnetic measurements, electron spin resonance, heat capacity, resistivity, and magnetocaloric effect as well as density functional theory (DFT), are presented for the compound NdRh2 (MgCu2-type structure). This compound was synthesized at a pressure of 8 GPa and a temperature of 1700 K. The magnetic properties of the material are shown to be determined by the high-temperature (over 400 K) spin polarization of the 4d Rh electrons and by the ferrimagnetic (FiM) interaction of Rh and Nd magnetic subsystems. Concurrently, the spontaneous magnetization of the spin polarization of 4d Rh electrons is ≈0.01μB/Rh, while the Nd magnetic moment is ≈1.7μB/Nd. This leads to complicated magnetic behavior with long range FiM order at TC≲7 K at zero field and with wide temperature range of spin fluctuations TC<T≲50 K. Specific heat and resistivity data provide corroboration of the spin fluctuation regime with the spin fluctuation temperature Θsf≈28.5 K. The optimal critical parameters were identified as β=1.18±0.02, γ=0.85±0.02, and TC≈40 K from modified Arrott plotting, which are distinct from any conventional universality class. The maximum magnetocaloric effect, when the magnetic field changes from 0 to 9 T, ΔH=9 T occurs at T≈11 K and the magnetic entropy change reaches −ΔSm=7.0 J (kg K)−1. In our DFT calculations, the FiM arrangement was obtained, with values of magnetic moments of Nd and Rh. Additionally, the Fermi surface was constructed.

Electron–electron scattering limits thermal conductivity of metals under extremely high electron temperatures

We report on the thermal transport properties of noble metals (gold, silver and copper) under conditions of extremely high electron temperatures (that are on the order of the Fermi energy). We perform parameter-free density functional theory calculations of the electron temperature-dependent electron–phonon coupling, electronic heat capacities, and thermal conductivities to elucidate the strong role played by the excitation of the low lying d-bands on the transport properties of the noble metals. Our calculations show that, although the three metals have similar electronic band structures, the changes in their electron–phonon coupling at elevated electron temperatures are drastically different; while electron–phonon coupling decreases in gold, it increases in copper and, it remains relatively unperturbed for silver with increasing electron temperatures of up to ∼60 000 K (or 5 eV). We attribute this to the varying contributions from acoustic and longitudinal phonon modes to the electron–phonon coupling in the three metals. Although their electron–phonon coupling changes with electron temperature, the thermal conductivity trends with electron temperature are similar for all three metals. For instance, the thermal conductivities for all three metals reach their maximum values (on par with the room-temperature values of some of the most thermally conductive semiconductors) at electron temperatures of ∼6000 K, and thereafter monotonically decrease due to the enhanced effect of electron–electron scattering for electronic states that are further away from the Fermi energy. As such, only accounting for electron–phonon coupling and neglecting electron–electron scattering can lead to large over-predictions of the thermal conductivities at extremely high electron temperatures. Our results shed light on the microscopic understanding of the electronic scattering mechanisms and thermal transport in noble metals under conditions of extremely high electron temperatures and, as such, are significant for a plethora of applications such as in plasmonic devices that routinely leverage hot electron transport.

Electronic heat capacity in bilayer P6 mmm borophene: Effects of a perpendicular electric field, excitonic effects, and dopants

In this work, we aim to control the electronic heat capacity (EHC) of bilayer P6 mmm borophene through a perpendicular electric field, excitonic effects, and external dopants. To achieve this, we employ the tight-binding model within a semi-classical framework. Our findings reveal a decrease in EHC under all stimuli due to decreased total electronic states in the system, while the coexistence of electric field and excitonic effects leads to an enhancement of EHC in the strong regime. Additionally, our study highlights a shift in the Schottky anomaly peak at low temperatures only in the strong regime of stimuli. This study is crucial for the design of thermoelectric materials based on borophene.

Construction of Ideal One-Dimensional Spin Chains by Topochemical Dehydration/Rehydration Route.

One-dimensional (1D) Heisenberg antiferromagnets are of great interest due to their intriguing quantum phenomena. However, the experimental realization of such systems with large spin S remains challenging because even weak interchain interactions induce long-range ordering. In this study, we present an ideal 1D S = 5/2 spin chain antiferromagnet achieved through a multistep topochemical route involving dehydration and rehydration. By desorbing three water molecules from (2,2'-bpy)FeF3(H2O)·2H2O (2,2'-bpy = 2,2'-bipyridyl) at 150 °C and then intercalating two water molecules at room temperature (giving (2,2'-bpy)FeF3·2H2O 1), the initially isolated FeF3ON2 octahedra combine to form corner-sharing FeF4N2 octahedral chains, which are effectively separated by organic and added water molecules. Mössbauer spectroscopy reveals significant dynamical fluctuations down to 2.7 K, despite the presence of strong intrachain interactions. Moreover, results from electron spin resonance (ESR) and heat capacity measurements indicate the absence of long-range order down to 0.5 K. This controlled topochemical dehydration/rehydration approach is further extended to (2,2'-bpy)CrF3·2H2O with S = 3/2 1D chains, thus opening the possibility of obtaining other low-dimensional spin lattices.

Melting properties of the refractory metals V and W and the binary VW alloy fully from first principles

We investigate the melting properties of the bcc refractory metals V and W, and the disordered equiatomic VW alloy from first principles. We show that thermal vibrations have a large impact on the electronic density of states (DOS) and thus considerably affect the electronic contribution to the free energy. For W, the impact of vibrations on the electronic free energy of solid and liquid is different. This difference substantially impacts the computed melting point and also triggers a large electronic heat capacity difference between solid and liquid. For V, although vibrations likewise affect the electronic free energy, the effect on the melting properties cancels out to a large degree. For the binary VW alloy we observe a similar impact as for W, but slightly weaker. The underlying physics is explained in terms of the electronic DOS of the solid and liquid phases. Based on our accurate first-principles results, we reveal critical limitations of the Sommerfeld approximation in predicting the electronic heat capacity difference between solid and liquid. Our results thus prompt us to scrutinize this approximation which is often used in phase diagram parametrizations in the CALPHAD approach, as well as for materials, such as W, that have a large electronic DOS difference between solid and liquid at the melting temperature. Published by the American Physical Society 2024

Development of a new analytical solution for electronic heat capacity for higher electron temperatures

A new analytical solution has been found for the electronic heat capacity of typical s-band metals. It is valid for high electron temperatures of the order of tens of kK, commonly reached in fs pulsed laser ablation. We have used the density of states (DOS) from the free-electron gas model (FEG) and a special type of function called polylogarithms. From the exact analytical solution, a third order Taylor expansion which works well up to 50kK could be derived. A new term was added to the DOS for d-band metals, which allowed us to find a new semi-analytical solution which predicts accurately the electronic heat capacity of Cu.

Electron and phonon temperatures: Application to the thermal-shock propagation in nanowires

Depending on the material properties of the system at hand, in some circumstances the application of a short pulse laser may initially bring a system into a highly non-equilibrium state wherein either the electron temperature may rise up while the lattice still remains cold, or conversely, because the heat capacity of electrons is usually different from that of lattice. In order to correctly describe the heat transport in those situations, therefore, one should properly split the non-equilibrium temperature into two different contributions: the electron temperature and the phonon temperature. By means of a recent two-temperature model (which fully agrees with the Maxwell-Cattaneo theory), in this paper we show that the values of those two temperatures may be always predictable during the thermal-shock propagation in nanowires, after having illustrated both that the employed theoretical model agrees with the basic tenets of continuum mechanics, and that it is mathematically well posed in the case of particular initial and boundary conditions. The main results of this paper could be used to deepen the concept of non-equilibrium temperature.

Computation insights of kagome structure for probing electronic and thermodynamic properties by applying external factors such as strain, spin-orbital coupling, and external magnetic field

In this study, we explored the electronic properties of a two-dimensional (2D) kagome lattice in the presence of an external magnetic field, spin-orbit coupling (SOC), and strain. Our focus was on investigating the energy-dependent behavior of the electronic heat capacity and paramagnetic spin susceptibility in response to changing factors. Employing the Green's function approach, we successfully determined the energy dependence of the electronic heat capacity and paramagnetic susceptibility using the tight-binding model. Notably, at low energies, the electronic heat capacity almost reaches the Schottky anomaly peak, while the paramagnetic susceptibility sharply decreases. Furthermore, we conducted a detailed investigation of the energy-dependent paramagnetic susceptibility and electronic heat capacity of a kagome lattice monolayer, considering the influences of SOC and magnetic field factors. Our investigation of the density of states (DOS) in the presence of SOC suggests that semimetal-to-insulator phase transitions occur. Additionally, throughout our study, we observed variations in the DOS spectrum, indicating the influence of both compressive and tensile strains. We found that these alterations, along with the splitting of levels under different conditions, led to changes in the material's electrical properties.

Optimizing thermoelectric performance of carbon-doped h-BN monolayers through tuning carrier concentrations and magnetic field

The thermoelectric properties of carbon-doped monolayer hexagonal boron nitride (h-BN) are studied using a tight-binding model employing Green function approach and the Kubo formalism. Accurate tight-binding parameters are obtained to achieve excellent fitting with Density Functional Theory results for doped h-BN structures with impurity type and concentration. The influence of carbon doping on the electronic properties, electrical conductivity, and heat capacity of h-BN is studied, especially under an applied magnetic field. Electronic properties are significantly altered by doping type, concentration, and magnetic field due to subband splitting, merging of adjacent subbands, and band gap reduction. These modifications influence the number, location, and magnitude of DOS peaks, generating extra peaks inside the band gap region. Heat capacity displays pronounced dependence on both magnetic field and impurity concentration, exhibiting higher intensity at lower dopant levels. Electrical conductivity is increased by double carbon doping compared to single doping, but is reduced at high magnetic fields because of high carrier scattering. The electronic figure of merit ZT increases with lower impurity concentration and is higher for CB versus CN doping at a given field strength. The power factor can be improved by increasing magnetic field and decreasing doping concentration. In summary, controlling doping and magnetic field demonstrates the ability to effectively engineer the thermoelectric properties of monolayer h-BN.

Tuning the electronic heat capacity and thermal Schottky anomaly of monolayer [formula omitted]-borophene via adsorbed gas molecules

Owing to the inherent inversion symmetry between five atoms {a,b,c,d,e} and metallic phase, β12-borophene possess fantastic physical properties, such as various electronic phase transitions in the presence of external perturbations. Here, the effect of adsorbed gas molecules (NH3, NO, NO2, and CO) on the electronic heat capacity (EHC) and thermal Schottky anomaly of β12-borophene is calculated employing the tight-binding model and the Green’s function approach. The results show that the gas-adsorbed EHC is enhanced with the dominant contribution of NO on individual {a,b,d,e} atoms, while it is NO2 on c atoms. However, EHC is suppressed when the molecule is adsorbed on the pair of boron atoms. Moreover, the enhancement of EHC is dominated by the simultaneous adsorption of NH3 on all atoms. On average, the pristine Schottky anomaly moves to the higher thermal energies upon the adsorption of gas molecules. These distinct differences originate from the generation of various new energy levels. This study provides a detailed understanding of β12-borophene response to the gas molecules for tuning field effect transistor-based gas sensors.

Observation of weak ferromagnetism in the antiferromagnetic host and large electronic heat capacity in β-Mn-type structured Mn3Al alloy

Numerous interesting features of antiferromagnets open up the possibility of designing new antiferromagnetic materials that can be useful for spintronic device applications. Here we present the structural, magnetic, thermal and electrical transport properties of polycrystalline Mn3Al alloys prepared by arc melting. Rietveld refinement of the room temperature X-Ray diffraction patterns reveals that the arc-melted Mn3Al crystallizes in a β Mn phase (space group 213). Detailed analysis of the magnetic data suggests for a dominant antiferromagnetic ordering. However, an in-homogenous magnetic disorder is observed in the system having a weak ferromagnetic phase in the antiferromagnetic host. In spite of the strong spin fluctuations in this system, the signature of spin glass-like nature in these alloys are not observed as probed by the frequency-dependent AC-Susceptibility measurements. Furthermore, the heat capacity was insensitive to the applied field of 3 Tesla with a negligible magnetic contribution suggesting a large electronic contribution to the heat capacity in these alloys. This work provides a useful insight into the tunable physical properties of the Heusler alloys for exploring antiferromagnetic based spintronic applications.

Low- and high-temperature heat capacity of metallic technetium

The heat capacity of technetium metal has been measured from 2.1 K to 293 K using relaxation calorimetry and the enthalpy increment up to 1700 K using drop calorimetry. The low-temperature calorimetry measurements revealed a superconducting transition temperature of TC = (7.76 ± 0.08) K. The zero-degree Debye temperature(θE) and the electronic heat capacity coefficient (γe) of the normal state were derived as (307 ± 5) K and (4.22 ± 0.20) mJ·K−2·mol−1, respectively. The standard entropy of the superconducting standard state was derived as Sm° (298.15) = (36.8 ± 1.3) J·K−1·mol−1. The fitting of enthalpy-increment data together with high-temperature heat capacity data reported in literature yielded a heat capacity equation up to 1700 K.

Heat capacity of one-dimensional Kane oscillator

The one-dimensional Kane oscillator in a thermal bath is studied. It is found that the heat capacity of Kane electrons is four times greater than the heat capacity of the one-dimensional harmonic oscillator for higher temperatures.

Electronic specific heat capacities and entropies from density matrix quantum Monte Carlo using Gaussian process regression to find gradients of noisy data.

We present a machine learning approach to calculating electronic specific heat capacities for a variety of benchmark molecular systems. Our models are based on data from density matrix quantum Monte Carlo, which is a stochastic method that can calculate the electronic energy at finite temperature. As these energies typically have noise, numerical derivatives of the energy can be challenging to find reliably. In order to circumvent this problem, we use Gaussian process regression to model the energy and use analytical derivatives to produce the specific heat capacity. From there, we also calculate the entropy by numerical integration. We compare our results to cubic splines and finite differences in a variety of molecules in which Hamiltonians can be diagonalized exactly with full configuration interaction. We finally apply this method to look at larger molecules where exact diagonalization is not possible and make comparisons with more approximate ways to calculate the specific heat capacity and entropy.