Thermodynamic Quantities Research Articles

Thermodynamics of a newly constructed black hole coupled with nonlinear electrodynamics and cloud of strings

This paper finds an exact singular black hole solution in the presence of nonlinear electrodynamics as the source of matter field surrounded by a cloud of strings in 4DAdS spacetime. Here, the presence of the cloud of string, the usual Bardeen solution, becomes singular. The obtained black hole solution interpolates with the AdS Letelier black hole in the absence of both the deviation parameter and magnetic charge and interpolates with the AdS Bardeen black hole in the absence of the deviation parameter and a cloud of strings parameter. We analyse the horizon structure and thermodynamics properties, including the stability of the resulting black hole, numerically and graphically. Thermodynamical quantities associated with the black hole get modified due to the nonlinear electrodynamics and cloud of strings. Moreover, we study the effect of a cloud of strings parameter, magnetic charge and deviation parameter on critical points and phase transition of the obtained black hole where the cosmological constant is treated as the thermodynamics pressure. The critical radius increases with increasing deviation parameter values and magnetic charge values. In contrast, the critical pressure and temperature decrease with increasing deviation parameters and magnetic charge values.

Quantum thermodynamics of the spin-boson model using the principle of minimal dissipation

Quantum thermodynamics of the spin-boson model using the principle of minimal dissipation

Heat capacity and quantum compressibility of dynamical spacetimes with thermal particle creation

This work continues the investigation in two recent papers on the quantum thermodynamics of spacetimes, (1) placing what was studied in [] for thermal quantum fields in the context of early universe cosmology, and (2) extending the considerations of vacuum compressibility of dynamical spaces treated in [] to dynamical spacetimes with thermal quantum fields. We begin with a warning that thermal equilibrium condition is not guaranteed to exist or maintained in a dynamical setting and thus finite temperature quantum field theory in cosmological spacetimes needs more careful considerations than what is often described in textbooks. A full description requires nonequilibrium quantum field theory in dynamical spacetimes using “in-in” techniques. A more manageable subclass of dynamics is where thermal equilibrium conditions are established at both the beginning and the end of evolution, where the in-thermal state and the out-thermal state are both well defined. Particle creation in the full history can then be calculated in this in-out asymptotically-stationary setup via the S-matrix transition amplitudes. Here we shall assume an in-vacuum state. It has been shown that if the intervening dynamics has an initial period of exponential expansion, such as in inflationary cosmology, particles created from the parametric amplification of the vacuum fluctuations in the initial vacuum will have a thermal spectrum measured at the out-state. Under these conditions finite temperature field theory can be applied to calculate the quantum thermodynamic quantities. Here we consider a massive conformal scalar field in a closed four-dimensional Friedmann-Lemaître-Robertson-Walker universe based on the simple analytically solvable Bernard-Duncan model. We calculate the energy density of particles created from an in-vacuum and derive the partition function. From the free energy we then derive the heat capacity and the quantum compressibility of these spacetimes with thermal particle creation. We end with some discussions and suggestions for further work in this program of studies. Published by the American Physical Society 2024

Dilatonic black holes in dRGT massive gravity

Motivated by high interest in Lorentz invariant massive gravity models known as the dRGT massive gravity, we discuss the dRGT massive gravity including the coupling term between dilaton scalar field and massive graviton, and present static and spherically symmetric solutions of dilatonic black holes in four and higher dimensional spacetime. Later, we investigate phase structure of these black hole solutions, and discover that the dilatonic black hole could possess two horizons, extreme and naked singularity black holes for the suitably parameters values. Calculating the conserved and thermodynamic quantities, we check the validity of the first law of thermodynamics.

Calibrating the Oxidative Capacity of Microdroplets

Recently, redox reactions have been reported to occur spontaneously in microdroplets. The origins of such reactivity are still debated, and any systematic correlation of the yield with the reactivity of the reactant is yet to be established. We report the simple, outer‐sphere, one‐electron oxidation of a series of ferrocene derivatives spanning oxidation potentials from −0.1 V to +0.8 V vs. Ag/AgCl generated via nebulization and measured by mass spectrometry of the ferrocenium ions. The reaction environments and dynamics in the droplets are complex, and it is still unclear whether such reactivity correlates with bulk thermodynamic values. Our key finding is that the ion yields decrease monotonically with the oxidation potential of the ferrocenes, which is a thermodynamic quantity. The ion yields emphatically do not obey the Nernstian ratio, revealing the redox processes in the droplets do not follow the assumptions of bulk steady‐state electrochemistry. Furthermore, oxidative competition in the mixture of several ferrocenes suggest a finite oxidative capacity or oxidant concentration. These results demonstrate that even though ion generation could be an out‐of‐equilibrium and kinetically limited process, the oxidative yield in microdroplets does correlate with thermodynamics, suggesting a possible free energy relationship between the kinetics and thermodynamics of the process.

Calibrating the Oxidative Capacity of Microdroplets.

Recently, redox reactions have been reported to occur spontaneously in microdroplets. The origins of such reactivity are still debated, and any systematic correlation of the yield with the reactivity of the reactant is yet to be established. We report the simple, outer-sphere, one-electron oxidation of a series of ferrocene derivatives spanning oxidation potentials from -0.1 V to +0.8 V vs. Ag/AgCl generated via nebulization and measured by mass spectrometry of the ferrocenium ions. The reaction environments and dynamics in the droplets are complex, and it is still unclear whether such reactivity correlates with bulk thermodynamic values. Our key finding is that the ion yields decrease monotonically with the oxidation potential of the ferrocenes, which is a thermodynamic quantity. The ion yields emphatically do not obey the Nernstian ratio, revealing the redox processes in the droplets do not follow the assumptions of bulk steady-state electrochemistry. Furthermore, oxidative competition in the mixture of several ferrocenes suggest a finite oxidative capacity or oxidant concentration. These results demonstrate that even though ion generation could be an out-of-equilibrium and kinetically limited process, the oxidative yield in microdroplets does correlate with thermodynamics, suggesting a possible free energy relationship between the kinetics and thermodynamics of the process.

Equilibrium Solubility of Sulfadiazine in (Acetonitrile + Ethanol) Mixtures: Determination, Correlation, Dissolution Thermodynamics, and Preferential Solvation

The equilibrium solubility of sulfadiazine (SD, 3) in several {acetonitrile (MeCN) + ethanol (EtOH)} mixtures at nine temperatures from T/K = (278.15 K to 318.15) has been determined by following the shake flask method. SD solubility increased with temperature-arising as well as with the MeCN proportion-increasing in the mixtures. Thus, x3 increased from 7.74 × 10−5 in neat EtOH to 6.20 × 10−4 in neat MeCN at T/K = 298.15. SD solubility was adequately correlated with a second-order multivariate equation as function of both mixtures composition and temperature. Moreover, two models including the Jouyban–Acree and Jouyban–Acree–van’t Hoff models were applied to mathematical SD solubility data modeling in solvent mixtures. The accuracy of each model is investigated by the mean relative deviations (MRD%) of the back-calculated solubility. A full predictive model was provided by training the Jouyban–Acree–van’t Hoff model with only seven experimental solubility data which provided excellent predictions with the MRD% of 3.7 %. All used models show a low MRD% values (< 4.0 %) for the calculated data indicating a good correlation of SD solubility data with the given mathematical models. By means of the van’t Hoff and Gibbs equations, the apparent thermodynamic quantities relative to SD dissolution and mixing processes, namely Gibbs energies, enthalpies, and entropies, were calculated and reported. Apparent dissolution quantities of SD were positive in all cases indicating endothermic and entropy-driven behaviors. A non-linear enthalpy–entropy relationship was observed for SD in the plot of SD dissolution enthalpy vs. Gibbs energy. Observed trend exhibits negative slope in the composition from neat EtOH to the mixture of 0.05 in mass fraction of MeCN indicating entropy-driving mechanism for this SD transfer process. Moreover, variant but positive slopes were found in the composition interval of 0.05 < w1 < 1.00 indicating enthalpy-driving mechanism for these SD transfer processes. Furthermore, the preferential solvation of SD by MeCN or EtOH was analyzed by using the inverse Kirkwood–Buff integrals. Thus, SD is preferentially solvated by EtOH molecules in EtOH-rich mixtures but preferentially solvated by MeCN in MeCN-rich mixtures. In this way, this research expands the literature investigations about the solubility of SD in some non-aqueous cosolvent mixtures conformed by MeCN and other alcohols.

Maxwell's equal area law for Vaidya-Bonner-de Sitter black hole under Lorentz invariance violation

In this study, we investigate the tunneling of fermions with arbitrary spin near the event horizon of a nonstationary Vaidya-Bonner-de Sitter (VBdS) black hole under Lorentz invariance violation (LIV). The modified Hawking temperature of VBdS black holes is calculated by using tortoise coordinate transformation, Feynman prescription, and Wentzel–Kramers–Brillouin approximation. By considering the cosmological constant as a thermodynamic pressure in the extended phase space, we construct a Maxwell's equal area law under LIV and study the phase transitions of VBdS black hole in , , and planes. The LIV increases the length of the liquid-gas coexistence region. The thermodynamic quantities such as the entropy, heat capacity, Helmholtz free energy, internal energy, enthalpy, and Gibbs free energy of the VBdS black hole are discussed. These quantities tend to increase under LIV. The stability of the black hole is also discussed in the presence of LIV.

Ideal Gas Thermodynamic Functions For NO From the Total Partition Sum and Its Moments

The total internal partition sum, Qint(T), and the translational partition sum, Qtrans(T), were computed for six isotopologues of NO: 14N16O, 15N16O, 14N18O, 14N17O, 15N18O, 15N17O. These were used to determine the total partition sum, Q(T), and its first and second moments, Q̃′T and Q̃″T. The total internal partition sum was computed using term values determined by Qu et al. [Mon. Not. R. Astron. Soc. 504, 5768–5777 (2021)] for 14N16O and those of Wong et al. [Mon. Not. R. Astron. Soc. 470, 882–897, (2017)] for the other isotopologues. These term values are the best available and hence provide the most accurate total internal partition sums and its first and second moments. The uncertainties in Qint(T), its moments, and the resulting thermodynamic functions were determined from the uncertainty in the term values and the uncertainty due to the convergence of the partition sum and its moments. From these quantities, the isobaric heat capacity, Helmholtz energy, entropy, enthalpy, Gibbs function, and the JANAF functions hef and gef, and their uncertainties, were computed on a 1 K grid from 1 to 9000 K. The data are compared with the literature values. The resulting thermodynamic quantities are the most accurate determined from direct summation of Q(T), Q̃′T, and Q̃″T.

Resistivity as a Witness of Local Crystal Growth Conditions

A detailed knowledge of the growth front geometry during physical vapor transport (PVT) growth of SiC single crystals is beneficial to achieve high quality n+ SiC substrates for power device applications. In this report we show how mapping of resistivity in SiC wafers can shed light on local growth conditions, which are very difficult-to-study in situ. We consider both thermodynamic quantities (absolute temperature T and partial pressure pN₂) and geometric characteristics of the growth surface relevant to growth kinetic parameters, namely atomic terrace width and atomic step velocity. Specifically, we show how an elevation map of the growth surface can be reconstructed from a spatially-resolved measurement of resistivity in a SiC wafer by integrating the spatial derivative of elevation with respect to the basal plane, which is assumed to be related to local resistivity through dependence of non-equilibrium nitrogen incorporation on the atomic step velocity.

Generalized entanglement capacity of de Sitter space

Near horizons, quantum fields of low spin exhibit densities of states that behave asymptotically like 1+1 dimensional conformal field theories. In effective field theory, imposing some short-distance cutoff, one can compute thermodynamic quantities associated with the horizon, and the leading cutoff sensitivity of the heat capacity is found to equal to the leading cutoff sensitivity of the entropy. One can also compute contributions to the thermodynamic quantities from the gravitational path integral. For the cosmological horizon of the static patch of de Sitter space, a natural conjecture for the relevant heat capacity is shown to equal the Bekenstein-Hawking entropy. These observations allow us to extend the well-known notion of the generalized entropy to a generalized heat capacity for the static patch of de Sitter (dS). The finiteness of the entropy and the nonvanishing of the generalized heat capacity suggest it is useful to think about dS as a state in a finite dimensional quantum gravity model that is not maximally uncertain. Published by the American Physical Society 2024

Force-Free Identification of Minimum-Energy Pathways and Transition States for Stochastic Electronic Structure Theories.

The accurate mapping of potential energy surfaces (PESs) is crucial to our understanding of the numerous physical and chemical processes mediated by atomic rearrangements, such as conformational changes and chemical reactions, and the thermodynamic and kinetic feasibility of these processes. Stochastic electronic structure theories, e.g., Quantum Monte Carlo (QMC) methods, enable highly accurate total energy calculations that in principle can be used to construct the PES. However, their stochastic nature poses a challenge to the computation and use of forces and Hessians, which are typically required in algorithms for minimum-energy pathway (MEP) and transition state (TS) identification, such as the nudged elastic band (NEB) algorithm and its climbing image formulation. Here, we present strategies that utilize the surrogate Hessian line-search method, previously developed for QMC structural optimization, to efficiently identify MEP and TS structures without requiring force calculations at the level of the stochastic electronic structure theory. By modifying the surrogate Hessian algorithm to operate in path-orthogonal subspaces and at saddle points, we show that it is possible to identify MEPs and TSs by using a force-free QMC approach. We demonstrate these strategies via two examples, the inversion of the ammonia (NH3) molecule and the nucleophilic substitution (SN2) reaction F- + CH3F → FCH3 + F-. We validate our results using Density Functional Theory (DFT)- and Coupled Cluster (CCSD, CCSD(T))-based NEB calculations. We then introduce a hybrid DFT-QMC approach to compute thermodynamic and kinetic quantities, free energy differences, rate constants, and equilibrium constants that incorporates stochastically optimized structures and their energies, and show that this scheme improves upon DFT accuracy. Our methods generalize straightforwardly to other systems and other high-accuracy theories that similarly face challenges computing energy gradients, paving the way for highly accurate PES mapping, transition state determination, and thermodynamic and kinetic calculations at significantly reduced computational expense.

Inferring general links between energetics and information with unknown environment

Identifying general links between energetics and information in realistic open quantum systems is a long-standing problem in quantum thermodynamics and quantum information processing. However, the generality of existing efforts is often impeded by their specific assumptions about environments. Here we address the problem by developing a trajectory-level thermodynamic inference theory to establish general links using just the knowledge of the system, enabling a single framework applicable to a diverse range of environments. Underpinning the framework is a notion of excess energy introduced for inferring the net energy gain of the system after completing an information processing trajectory. We show that fluctuation behaviors of the excess energy encode general links between energetics and information with a conceptual advantage that they completely avoid assumptions about environments and system-environment coupling forms. Crucially, we obtain a single thermodynamic inequality that integrates upper bounds on heat dissipation and extracted work in terms of system's information content change, providing complementary constraints that greatly expand the context of existing well-adopted results based on the second law of thermodynamics. We also uncover lower bounds on the precision of the fluctuating system's energy and information content changes in terms of their Fano factors and a correlation function between them. By extending relations between energetics and information to higher-order fluctuations, we thus reveal a trade-off that a more precise inference of energy or information content changes requires a looser energetic-information link. We showcase the implications of these general links in a number of quantum information and thermodynamic tasks of application relevance. Our framework provides a toolkit for analyzing the interplay between energetics and information from the trajectory level in generic quantum systems, thereby adding an indispensable structure to the thermodynamics of information. Published by the American Physical Society 2024

Thermal fluctuations, deflection angle, and greybody factor of a high-dimensional Schwarzschild black hole in scalar–tensor–vector gravity

In this study, we examined the thermal fluctuations, deflection angle, and greybody factor of a high-dimensional Schwarzschild black hole in scalar–tensor–vector gravity (STVG). We calculated some thermodynamic quantities related to the correction of the black hole entropy caused by thermal fluctuations and discussed the effect of the correction parameters on these quantities. By analyzing the changes in the corrected specific heat, we found that thermal fluctuations made the small black hole more stable. It is worth noting that the STVG parameter did not affect the thermodynamic stability of this black hole. Additionally, by utilizing the Gauss–Bonnet theorem, the deflection angle was obtained in the weak field limit, and the effects of the two parameters on the results were visualized. Finally, we calculated the bounds on the greybody factor of a massless scalar field. We observed that as the STVG parameter around the black hole increased, the weak deflection angle became larger, and more scalar particles can reach infinity. However, the spacetime dimension has the opposite effect on the STVG parameter on the weak deflection angle and greybody factor.

Effect of cyclodextrin modification on complexation thermodynamics with hexadecyltrimethylammonium cation with emphasis on subsequent surfactant micellization

Surfactant-cyclodextrin based complexes, are ideal guest-hosts for fundamental studies since both surfactant hydrophobic region with head group, and cyclodextrin cavity can be systematically varied. This allows, better understanding of the contributions that different chemical entities do to the stabilization of the complex and subsequent surfactant micellization. We studied systematically the interaction of hexadecyltrimethylammonium bromide (▪) with native α-, β- and γ-CDs, 2-hydroxypropylated and methylated α- and β-CDs, using isothermal titration calorimetry (ITC), measuring below critical micellization concentration (CMC) at least at three temperatures in the range (288.15 to 318.15) K. Data were treated simultaneously allowing the estimation of thermodynamically consistent temperature dependences of the equilibrium constant, the enthalpy and heat capacity for the inclusion complex formation. The data for cation/CD interaction were analysed mostly by the sequential binding model with 1:1 and 1:2 (cation:CD) stoichiometries, while some cation-CD combinations were examined using only 1:1, or more complicated 1:1, 2:1 and 2:2 stoichiometries. Thermodynamic quantities for complexation are discussed in terms of structural features, their temperature dependence with previous literature being examined. The shift of the CMC in presence of CDs was calculated founding large discrepancies with data in the literature. An extended mass-action chemical equilibrium model is proposed including free surfactant, free CD, complexes of the above mention stoichiometries, also including micelle, surfactant-cyclodextrin complexes of higher order stoichiometry, similar to that found for sodium dodecylsulfate-CDs systems. The new model provides a qualitative match with our own calorimetric titration curves measured above CMC for all studied ▪/CD combinations, and matches quantitatively with literature CMC values.

Molecular Properties of Monoaminergic Catecholamines in Water.

Three neurotransmitters belonging to catecholamines (dopamine, noradrenaline, adrenaline) and related α-amino acids (DOPA and tyrosine) were studied by quantum-chemical ab initio and DFT calculations using B3LYP and DLPNO-CCSD(T) methods in water. In addition to the three canonical forms, zwitterionic forms were also investigated, each in three oxidation states (molecular cation L+, electroneutral molecule L0, and molecular anion L-). Each species was subjected to geometry optimization followed by vibrational analysis. Electronic properties (adiabatic ionization energy, electron affinity, chemical hardness, molecular electronegativity, electrophilicity index, dipole moment, electric polarizability, and quadrupole moment) and standard thermodynamic quantities (inner energy, entropy, enthalpy, and Gibbs energy) were evaluated, which allows the absolute oxidation and reduction potentials to be calculated. The absolute reduction potential (ARP) was found to correlate with the electrophilicity index ω along a straight line. Moreover, in addition to the standard expression for the absolute redox potential using reaction Gibbs energy, an approximation based on ionization energy and/or electron affinity was also tested. The main finding is that dopamine is a much weaker oxidizing agent with the ARP = 0.99 V relative to tyrosine with ARP = 1.38 V for canonical structures in water. This is also true for the zwitterionic structures in water: for dopamine ARP = 0.63 V is much lower relative to tyrosine with ARP = 1.31 V. The protonated form (DOPAH+) has the highest ARP = 2.02 V. Prediction of the redox potentials is an important factor influencing antioxidant (EC50) and/or antireductant activity. Based on 16 molecular properties for 20 molecules (320 entries), advanced statistical methods (cluster analysis, principal component analysis, pair-correlation) reveal that several groups of similarity exist: {dopamine-noradrenaline}, different from {adrenaline-DOPA-(tyrosine)} and zwitterionic forms of {dopamine-noradrenaline-adrenaline}.

A Study of Micellar Catalyses on Oxidation of Glycine by QDC in the Presence of Sodium Dodecyl Sulphate (SDS) in Aqueous Perchloric Acid Medium

Aims: To study the micellar effect of SDS on the oxidation of glycine by Quinolinium Dichromate (QDC) in perchloric acid medium. Background: Among the amino acids, glycine plays a major role in multiple metabolic reactions, such as glutathione synthesis and one-carbon metabolism. The oxidation of glycine has received importance because it is the major neurotransmitter inhibitor in the spinal cord and brainstem. In the oxidation process of amino acids, highly toxic chromium (VI) compounds are converted into non-toxic chromium (III) by quinolinium dichromate (QDC) oxidant in an appropriate pH value medium. Objective: 1. To study the catalytic role of anionic surfactant (SDS) on the oxidation of glycine by QDC through micellization, evaluation of critical micelles concentration (CMC) in the presence and absence of glycine and other surface properties along with thermodynamic quantities. 2. Determination of rate constant and order of reaction with respect to QDC, glycine, acid and surfactant which will help to study the kinetics of the reaction 3. Analysis of oxidation product by FT-IR and calculation of activation parameters. 4. Synthesis of oxidant (QDC) and its characterization by UV-Visible spectrophotometer and NMR spectroscopy. Results: First-order kinetics was observed with respect to oxidant, glycine and hydrogen ions. The rate of reaction increased remarkably with an increase in the concentration of surfactant (SDS). The kinetic results show that the ionic strength variation does not have any significant effect on the rate whereas the increase in the dielectric constant of the medium shows a remarkable effect on the rate constant. From stoichiometry study, it was found that 2 moles of oxidant (QDC) consumed 3 moles of glycine to produce aldehyde (Formaldehyde). Conclusion: The observed negative value of (ΔS) entropy of activation and positive (ΔH) enthalpy of activation suggests a more ordered activated complex formation and highly solvated transition state. The kinetics of the reaction in a perchloric acid medium is found to be accelerated in the presence of surfactant (SDS). The kinetics of the reaction follow pseudo first-order decay of Cr(VI) species (QDC), a unity dependence of rate on glycine and perchloric acid. The oxidation product formaldehyde was identified by FTIR. NMR spectrum analysis of synthesized QDC shows a resemblance with pure QDC.

Nonlinear wave propagation in large extra spatial dimensions and the blackbody thermal laws

Abstract Nonlinear wave propagation in large extra spatial dimensions (on and above d = 2) is investigated in the context of nonlinear electrodynamics theories that depend exclusively on the invariant F ( = − ( 1 / 4 ) F μ ν F μ ν ) . In this vein, we consider propagating waves under the influence of external uniform electric and magnetic fields. Features related to the blackbody radiation in the presence of a background constant electric field such as the generalization of the spectral energy density distribution and the Stefan–Boltzmann law are obtained. Interestingly enough, anisotropic contributions to the frequency spectrum appear in connection to the nonlinearity of the electromagnetic field. In addition, the long wavelength regime and Wien’s displacement law in this situation are studied. The corresponding thermodynamics quantities at thermal equilibrium, such as energy, pressure, entropy, and heat capacity densities are contemplated as well.

Generalized Linear Response Theory for the Full Quantum Work Statistics.

We consider a quantum system driven out of equilibrium via a small Hamiltonian perturbation. Building on the paradigmatic framework of linear response theory (LRT), we derive an expression for the full generating function of the dissipated work. Remarkably, we find that all information about the distribution can be encoded in a single quantity, the standard relaxation function in LRT, thus opening up new ways to use phenomenological models to study nonequilibrium fluctuations in complex quantum systems. Our results establish a number of refined quantum thermodynamic constraints on the work statistics that apply to regimes of perturbative but arbitrarily fast protocols, and do not rely on assumptions such as slow driving or weak coupling. Finally, our approach uncovers a distinctly quantum signature in the work statistics that originates from underlying zero-point energy fluctuations. This causes an increased dispersion of the probability distribution at short driving times, a feature that can be probed in efforts to witness nonclassical effects in quantum thermodynamics.

Probing coherent quantum thermodynamics using a trapped ion

Quantum thermodynamics is aimed at grasping thermodynamic laws as they apply to thermal machines operating in the deep quantum regime, where coherence and entanglement are expected to matter. Despite substantial progress, however, it has remained difficult to develop thermal machines in which such quantum effects are observed to be of pivotal importance. In this work, we demonstrate the possibility to experimentally measure and benchmark a genuine quantum correction, induced by quantum friction, to the classical work fluctuation-dissipation relation. This is achieved by combining laser-induced coherent Hamiltonian rotations and energy measurements on a trapped ion. Our results demonstrate that recent developments in stochastic quantum thermodynamics can be used to benchmark and unambiguously distinguish genuine quantum coherent signatures generated along driving protocols, even in presence of experimental SPAM errors and, most importantly, beyond the regimes for which theoretical predictions are available (e.g., in slow driving).