Ehrenfest Equations Research Articles

Static black hole in minimal Horndeski gravity with Maxwell and Yang-Mills fields and some aspects of its thermodynamics

In this work we obtain a static spherically symmetric charged black hole solution in the framework of minimal Horndeski gravity with additional Maxwell and Yang-Mills fields. The obtained solution is examined; in particular, its asymptotics are studied. Thermodynamics of the black hole is investigated, namely, we use an effective surface gravity to derive black hole temperature. To obtain the first law of black hole thermodynamics, the Wald method is applied. We also use the extended thermodynamics approach, namely, it allows us to derive the Smarr relation, Gibbs free energy, and the thermal equation of state. The study of thermal values in the extended space shows rich phase behavior, in particular, the domain where the first-order phase transition takes place and the critical point with the second-order phase transition. We also study thermal behavior near the critical point, obtain critical exponents, and analyze the Ehrenfest equations at the critical point. Finally, we calculate the Prigogine-Defay ratio confirming the conclusion about the second-order phase transition at the critical point. Published by the American Physical Society 2024

Total angular momentum conservation in Ehrenfest dynamics with a truncated basis of adiabatic states.

We show that standard Ehrenfest dynamics does not conserve linear and angular momentum when using a basis of truncated adiabatic states. However, we also show that previously proposed effective Ehrenfest equations of motion [M. Amano and K. Takatsuka, "Quantum fluctuation of electronic wave-packet dynamics coupled with classical nuclear motions," J. Chem. Phys. 122, 084113 (2005) and V. Krishna, "Path integral formulation for quantum nonadiabatic dynamics and the mixed quantum classical limit," J. Chem. Phys. 126, 134107 (2007)] involving the non-Abelian Berry force do maintain momentum conservation. As a numerical example, we investigate the Kramers doublet of the methoxy radical using generalized Hartree-Fock with spin-orbit coupling and confirm that angular momentum is conserved with the proper equations of motion. Our work makes clear some of the limitations of the Born-Oppenheimer approximation when using abinitio electronic structure theory to treat systems with unpaired electronic spin degrees of freedom, and we demonstrate that Ehrenfest dynamics can offer much improved, qualitatively correct results.

Thermodynamic quantities and phase transitions of five-dimensional de Sitter hairy spacetime* *Supported by the National Natural Science Foundation of China (12075143)

In this study, we take the mass, electric charge, hair parameter, and cosmological constant of five-dimensional de Sitter hairy spacetime as the state parameters of the thermodynamic system, and when these state parameters satisfy the first law of thermodynamics, the equivalent thermodynamic quantities of spacetime and the Smarr relation of five-dimensional de Sitter hairy spacetime are obtained. Then, we study the thermodynamic characteristics of the spacetime described by these equivalent thermodynamic quantities and find that de Sitter hairy spacetime has a phase transition and critical phenomena similar to those of van de Waals systems or charged AdS black holes. It is shown that the phase transition point of de Sitter hairy spacetime is determined by the ratio of two event horizon positions and the cosmic event horizon position. We discuss the influence of the hair parameter and electric charge on the critical point. We also find that the isochoric heat capacity of the spacetime is not zero, which is consistent with the ordinary thermodynamic system but differs from the isochoric heat capacity of AdS black holes, which is zero. Using the Ehrenfest equations, we prove that the critical phase transition is a second order equilibrium phase transition. Research on the thermodynamic properties of five-dimensional de Sitter hairy spacetime lays a foundation for finding a universal de Sitter spacetime thermodynamic system and studying its thermodynamic properties. Our universe is an asymptotically dS spacetime, and the thermodynamic characteristics of de Sitter hairy spacetime will help us understand the evolution of spacetime and provide a theoretical basis to explore the physical mechanism of the accelerated expansion of the universe.

Dynamical Simulations of Carotenoid Photoexcited States Using Density Matrix Renormalization Group Techniques.

We present a dynamical simulation scheme to model the highly correlated excited state dynamics of linear polyenes. We apply it to investigate the internal conversion processes of carotenoids following their photoexcitation. We use the extended Hubbard-Peierls model, , to describe the π-electronic system coupled to nuclear degrees of freedom. This is supplemented by a Hamiltonian, , that explicitly breaks both the particle-hole and two-fold rotation symmetries of idealized carotenoid structures. The electronic degrees of freedom are treated quantum mechanically by solving the time-dependent Schrödinger equation using the adaptive time-dependent DMRG (tDMRG) method, while nuclear dynamics are treated via the Ehrenfest equations of motion. By defining adiabatic excited states as the eigenstates of the full Hamiltonian, , and diabatic excited states as eigenstates of , we present a computational framework to monitor the internal conversion process from the initial photoexcited 11Bu+ state to the singlet triplet-pair states of carotenoids. We further incorporate Lanczos-DMRG to the tDMRG-Ehrenfest method to calculate transient absorption spectra from the evolving photoexcited state. We describe in detail the accuracy and convergence criteria for DMRG, and show that this method accurately describes the dynamical processes of carotenoid excited states. We also discuss the effect of the symmetry-breaking term, , on the internal conversion process, and show that its effect on the extent of internal conversion can be described by a Landau-Zener-type transition. This methodological paper is a companion to our more explanatory discussion of carotenoid excited state dynamics in Manawadu, D.; Georges, T. N.; Barford, W. Photoexcited State Dynamics and Singlet Fission in Carotenoids. J. Phys. Chem. A 2023, 127, 1342.

Photoexcited State Dynamics and Singlet Fission in Carotenoids.

We describe our simulations of the excited state dynamics of the carotenoid neurosporene, following its photoexcitation into the "bright" (nominally 11Bu+) state. To account for the experimental and theoretical uncertainty in the relative energetic ordering of the nominal 11Bu+ and 21Ag- states at the Franck-Condon point, we consider two parameter sets. In both cases, there is ultrafast internal conversion from the "bright" state to a "dark" singlet triplet-pair state, i.e., to one member of the "2Ag" family of states. For one parameter set, internal conversion from the 11Bu+ to 21Ag- states occurs via the dark, intermediate 11Bu- state. In this case, there is a cross over of the 11Bu+ and 11Bu- diabatic energies within 5 fs and an associated avoided crossing of the S2 and S3 adiabatic energies. After the adiabatic evolution of the S2 state from predominately 11Bu+ character to predominately 11Bu- character, there is a slower nonadiabatic transition from S2 to S1, accompanied by an increase in the population of the 21Ag- state. For the other parameter set, the 21Ag- energy lies higher than the 11Bu+ energy at the Franck-Condon point. In this case, there is cross over of the 21Ag- and 11Bu+ energies and an avoided crossing of the S1 and S2 energies, as the S1 state evolves adiabatically from being of 11Bu+ character to 21Ag- character. We make a direct connection from our predictions to experimental observables by calculating the time-resolved excited state absorption. For the case of direct 11Bu+ to 21Ag- internal conversion, we show that the dominant transition at ca. 2 eV, being close to but lower in energy than the T1 to T1* transition, can be attributed to the 21Ag- component of S1. Moreover, we show that it is the charge-transfer exciton component of the 21Ag- state that is responsible for this transition (to a higher-lying exciton state), and not its triplet-pair component. These simulations are performed using the adaptive tDMRG method on the extended Hubbard model of π-conjugated electrons. The Ehrenfest equations of motion are used to simulate the coupled nuclei dynamics. We next discuss the microscopic mechanism of "bright" to "dark" state internal conversion and emphasize that this occurs via the exciton components of both states. Finally, we describe a mechanism relying on torsional relaxation whereby the strongly bound intrachain triplet-pairs of the "dark" state may undergo interchain exothermic dissociation.

Did S. P. Timoshenko and P. Ehrenfest Overestimate the Importance of the Fourth-Order Time Derivative in Their Beam Theory?

Abstract In this study, we investigate the importance of the fourth-order time derivative that appears in the equations derived by Jacques Antoine Charles Bresse in 1859, as well as in equations that were derived by Stephen Prokofievich Timoshenko and Paul Ehrenfest during years 1912 and 1913 and reported by Timoshenko in the 1916 book on the theory of elasticity in the Russian language and then in two papers dated 1920 and 1921, in English. The first part of the study demonstrates that Timoshenko and Ehrenfest did not overestimate the importance of the fourth-order derivative term in their equations. The second part deals with the debate on the so-called second spectrum attendant in the original set of equations. It is shown that in the truncated Timoshenko—Ehrenfest equations—which is asymptotically consistent with elasticity theory—“the second spectrum” issue does not arise. Thus, the two parts of this study are intricately interrelated with each other.

Phase transition grade and microstructure of AdS black holes in massive gravity

Considering that under the framework of the massive gravity theory, the interaction between the mass gravitons and Schwarzschild black hole (BH) could make it carry a scalar charge, the phase transition process caused by this scalar charge is investigated in this analysis. The phase transition grade and microstructure of those BHs are investigated from both macroscopic and microscopic points of view. From the macroscopic point of view, it is found that Ehrenfest equations are satisfied at the phase transition critical point, which implies that the phase transition grade of those BHs is second-order. Based on the BH molecules model and Landau continuous phase transition theory, the phase transition of those BHs from the microcosmic point of view is analyzed. The critical exponents obtained from the two perspectives are consistent. By investigating the Ruppeiner geometry, the microstructure feature of those BHs is revealed. These results suggest that the phase transition of BH in massive gravity is a standard second-order phase transition at the critical point, and the microscopic details of those BHs are different from the Reissner–Nordström AdS BH in standard Einstein gravity.

Singlet Triplet-Pair Production and Possible Singlet-Fission in Carotenoids.

Internal conversion from the photoexcited state to a correlated singlet triplet-pair state is believed to be the precursor of singlet fission in carotenoids. We present numerical simulations of this process using a π-electron model that fully accounts for electron–electron interactions and electron–nuclear coupling. The time-evolution of the electrons is determined rigorously using the time-dependent density matrix renormalization group method, while the nuclei are evolved via the Ehrenfest equations of motion. We apply this to zeaxanthin, a carotenoid chain with 18 fully conjugated carbon atoms. We show that the internal conversion of the primary photoexcited state, S2, to the singlet triplet-pair state occurs adiabatically via an avoided crossing within ∼50 fs with a yield of ∼60%. We further discuss whether this singlet triplet-pair state will undergo exothermic versus endothermic intra- or interchain singlet fission.

Thermally driven polaron transport in conjugated polymers

We present a hybrid quantum-classical simulation of charge-polaron transport in conjugated polymers. The charge, which couples to the angular rotations of the monomers, is modeled via the time-dependent Schr\"odinger equation, while the monomers are treated classically via the Ehrenfest equations of motion. In addition, the system is thermalized by assuming that the monomers are subject to Brownian fluctuations modeled by the Langevin equation. Charge coupling to the monomer rotations localizes the particle into a Landau polaron, while the thermal fluctuations of the monomers causes polaron dynamics. The emergent low-energy scale of the model is the polaron reorganization energy, $E_r$, and thus $T_r = E_r/k_B$ is a convenient scale for the low-temperature dynamics. We investigate two types of dynamics -- both relevant for temperatures $T < T_r$. In the lower temperature regime the system remains in the same quasidiabatic state, corresponding to activationless polaron diffusion as the polaron crawls stochastically along the chain. As the temperature is raised, however, there is a cross-over to an additional activated transfer process which corresponds to hopping between diabatic states. We show that these processes exhibit Landau-Zener type dynamics. We note that as our model is general, it equally applies to exciton-polaron (i.e., energy) transport in conjugated polymers, and to charge and exciton polaron transport in quasi one-dimensional molecular stacks.

Thermodynamics and phase transition of topological dS black holes with a nonlinear source

We discuss black hole solutions of Einstein-Λ gravity in the presence of nonlinear electrodynamics in dS spacetime. Considering the correlation of the thermodynamic quantities respectively corresponding to the black hole horizon and cosmological horizon of dS spacetime and taking the region between the two horizons as a thermodynamic system, we derive effective thermodynamic quantities of the system according to the first law of thermodynamics, and investigate the thermodynamic properties of the system under the influence of nonlinearity parameter α. It is shown that nonlinearity parameter α influences the position of the black hole horizon and the critical state of the system, and along with electric charge has an effect on the phase structure of the system, which is obvious, especially as the effective temperature is below the critical temperature. The critical phase transition is proved to be second-order equilibrium phase transition by using the Gibbs free energy criterion and Ehrenfest equations.

Flutter of a beam in supersonic flow: truncated version of Timoshenko–Ehrenfest equation is sufficient

This paper deals with flutter due to gas flow of a uniform and homogeneous beam with shear deformation and rotary inertia effects taken into account. It utilizes the truncated, consistent Timoshenko–Ehrenfest beam model in contrast to the original Timoshenko–Ehrenfest equations. Omission of the fourth order derivative term in the governing differential equation of the original equations of Timoshenko and Ehrenfest is shown to be more consistent than retaining it as is done in the original Timoshenko–Ehrenfest set. The original Timoshenko–Ehrenfest equations are exposed in almost all textbooks published after 1921. However, this paper shows that these original equations are unnecessarily overcomplicated, and simpler set is consistent. This truncation significantly simplifies the analytical and numerical analyses considerably and agrees with the principle of parsimony, i.e. the most acceptable explanation of a phenomenon is the simplest, involving the fewest entities and assumptions. The critical flutter velocities are compared with the results obtained by using the original set of Timoshenko–Ehrenfest equations.

A brief history of first-order shear-deformable beam and plate models

This paper presents a brief history of beam and plate models in elasticity, that take into account the rotary inertia and shear contribution. We show that Bresse (1859) already in the mid XIXth century rigorously derived the set of equations for curved shear and axially extensible beams in dynamics, although without shear correction factor. When restricted to straight beams, Bresse (1859) obtained a two-field beam kinematics composed of independent deflection and rotation variables. These equations have been generalized by Timoshenko (1913; 1916; 1920; 1921; 1922), without direct reference to the works of Bresse, by a slight modification of the shear stiffness, that incorporates a shear correction factor generally different from unity. The calibration of the shear correction factor with respect to three-dimensional elasticity solutions has been elaborated jointly by Ehrenfest and Timoshenko in the second decade of the XXth century (the calibration of the shear correction factor for rectangular cross section has been finalized by Timoshenko in 1922, even if the basic results were available in his letter dated from 1913, in collaboration with Ehrenfest). Whereas Bresse-Timoshenko–Ehrenfest equations have been elaborated mainly during more than half a century between 1859 and 1922 (even if researches on shear beam theories were still active), the Uflyand–Mindlin plate theory has been built in a more compact period, mainly between 1944 and 1951. Whereas Reissner (1944, 1945) developed a static (or stress-based) formulation, the kinematic theory of Uflyand-Mindlin plate model has been first elaborated by Bolle (1947) and Hencky (1947) for static setting, before the full generalization to dynamics by Uflyand a year later, in 1948, and its complete variational derivation by Mindlin (1951). A lot of efforts were spent since almost half of the century to calibrate the shear correction factor and to enrich the kinematics of Uflyand-Mindlin plate theory. It is quite surprising that the shear correction factors of both the Bresse–Timoshenko–Ehrenfest beam model and its Uflyand-Mindlin plate analogy were already implicitly available in the paper of Timoshenko (1922), performed, in his own testimony with Ehrenfest.

Decoherence of nonrelativistic bosonic quantum fields

We present a generic Markovian master equation inducing the gradual classicalization of a bosonic quantum field. It leads to the decoherence of quantum superpositions of field configurations, while leaving the Ehrenfest equations for both the field and the mode-variables invariant. We characterize the classicalization analytically and numerically, and show that the semiclassical field dynamics is described by a linear Boltzmann equation in the functional phase space of field configurations.

Extended phase-space thermodynamics of black holes in massive gravity

We study the extended phase-space thermodynamics of black holes in massive gravity. Particularly, we examine the critical behavior of this black hole using the extended phase-space formalism. Extended phase-space can be defined as one in which the cosmological constant should be treated as a thermodynamic pressure and its conjugate variable as a thermodynamic volume. In this phase-space, we derive the black hole equation of state, the critical pressure, the critical volume and the critical temperature at the critical point. We also derive the critical ratio of this black hole. Moreover, we derive the black hole reduced equation of state in terms of the reduced pressure, the reduced volume and the reduced temperature. Furthermore, we examine the Ehrenfest equations of black holes in massive gravity in the extended phase-space at the critical point. We show that the Ehrenfest equations are satisfied on this black hole and the black hole encounters a second-order phase transition at the critical point in the said phase-space. This is re-examined by evaluating the Pregogine–Defay ratio [Formula: see text]. We determine the value of this ratio is [Formula: see text]. The outcome of this study is completely analogous to the nature of liquid–gas phase transition at the critical point. This investigation also further gives us the profound understanding between the black hole of massive gravity with the liquid–gas system.

Entropy of the electrically charged hairy black holes

In this paper, we discuss the effective thermodynamic quantities of higher dimensional electrically charged hairy black holes in de Sitter spacetime, considering the correlation between the black hole horizon and the cosmological horizon. Our results show that, the interaction term determined by the position of the two horizons could significantly contribute to the total entropy of de Sitter spacetime. Moreover, different from the case in AdS spacetime, we find both zero-order and second-order phase transitions under certain conditions, with the absence of first-order phase transition in the electrically charged hairy black holes. These results are strongly supported by the classification of phase transition in Ehrenfest’s equations. More interestingly, our analysis demonstrates the validity of the Ehrenfest equations at the critical point, and futhermore indicates the similarity of Prigogine–Defay (PD) ratio between ECBH spacetime and AdS spacetime.

Coupled-Trajectory Mixed Quantum-Classical Algorithm: A Deconstruction

We analyze a mixed quantum-classical algorithm recently derived from the exact factorization equations [Min, Agostini, Gross, PRL 115, 073001 (2015)] to show the role of the different terms in the algorithm in bringing about decoherence and wavepacket branching. The algorithm has the structure of Ehrenfest equations plus a "coupled-trajectory" term for both the electronic and nuclear equations, and we analyze the relative roles played by the different nonadiabatic terms in these equations, including how they are computed in practice. In particular, we show that while the coupled-trajectory term in the electronic equation is essential in yielding accurate dynamics, that in the nuclear equation has a much smaller effect. A decoherence time is extracted from the electronic equations and compared with that of augmented fewest-switches surface-hopping. We revisit a series of nonadiabatic Tully model systems to illustrate our analysis.

Communication: Glass transition and melting lines of an ionic liquid.

The phase diagram of the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesufonyl)imide, [Pyrr1,4][NTf2], was explored by synchroton X-ray diffraction and Raman scattering measurements as a function of temperature and pressure. Glass transition Tg(p) and melting Tm(p) temperatures were obtained from atmospheric pressure up to ca. 2.0 GPa. We found that both the Tg(p) and Tm(p) curves follow essentially the same pressure dependence. The similarity of pressure coefficients, dTg/dp ≈ dTm/dp, is explained within the non-equilibrium thermodynamics approach for the glass transition by assuming that one of the Ehrenfest equations is appropriated for Tg(p), whereas Tm(p) follows the Clausius-Clapeyron equation valid for the first-order transitions. The results highlight that ionic liquids are excellent model systems to address fundamental questions related to the glass transition.

Many-particle quantum hydrodynamics: Exact equations and pressure tensors

In the first part of this paper, the many-particle quantum hydrodynamics (MPQHD) equations for a system containing many particles of different sorts are derived exactly from the many-particle Schrodinger equation. It includes the derivation of the many-particle continuity equations (MPCE), many-particle Ehrenfest equations of motion (MPEEM), and many-particle quantum Cauchy equations (MPQCE) for any of the different particle sorts and for the total particle ensemble. The new point in our analysis is that we consider a set of arbitrary particles of different sorts in the system. In MPQCEs, there appears a quantity called pressure tensor. In the second part of this paper, we analyze two versions of this tensor in depth -- the Wyatt pressure tensor and the Kuzmenkov pressure tensor. There are different versions because there is a gauge freedom for the pressure tensor similar to that for potentials. We find that the interpretation of all quantities contributing to the Wyatt pressure tensor is understandable but for the Kuzmenkov tensor, it is difficult. Furthermore, the transformation from Cartesian coordinates to cylindrical coordinates for the Wyatt tensor can be done in a clear way, but for the Kuzmenkov tensor, it is rather cumbersome.

‘Second’ Ehrenfest equation for second order phase transition under hydrostatic pressure

It is shown that the fundamental conditions for the second-order phase transitions and , from which the two Ehrenfest equations follow (the ‘usual’ and the ‘second’ ones), are realised only at zero hydrostatic pressure (). At the volume jump ΔV at the transition is proportional to the pressure and to the jump of the compressibility ΔζV, whereas the entropy jump ΔS is proportional to the pressure and to the jump of the thermal expansion coefficient ΔαV. This means that at non-zero hydrostatic pressure the phase transition is of the first order and is described by the Clausius–Clapeyron equation. At small pressure this equation coincides with the ‘second’ Ehrenfest equation . At high P, the Clausius–Clapeyron equation describes qualitatively the caused by the crystal compression positive curvature of the dependence.

Phase transition and thermodynamic stability in extended phase space and charged Hořava–Lifshitz black holes

For charged black holes in Horava-Lifshitz gravity, a second order phase transition takes place in extended phase space where the cosmological constant is taken as thermodynamic pressure. We relate the second order nature of phase transition to the fact that the phase transition occurs at a sharp temperature and not over a temperature interval. Once we know the continuity of the first derivatives of the Gibbs free energy, we show that all the Ehrenfest equations are readily satisfied. We study the effect of the perturbation of the cosmological constant as well as the perturbation of the electric charge on thermodynamic stability of Horava-Lifshitz black hole. We also use thermodynamic geometry to study phase transition in extended phase space. We investigate the behavior of scalar curvature of Weinhold, Ruppeiner, and Quevedo metric in extended phase space of charged Horava-Lifshitz black holes. It is checked if these curvatures could reproduce the result of specific heat for the phase transition.