A study of the one-dimensional molecular chain (MC) with two single-particle degenerate states is presented. We establish connection of the MC with the Ising model with phononic interactions and investigate properties of the model using a transfer matrix method. The transfer matrix method offers a promising pathway for simulating such materials properties. The role of degeneracy of states and phononic interaction being made explicit. We analyze regimes of the system and parameters of the occurring crossover. Here, we present exact results for the magnetization per spin, the correlation function and the effective volume of the system. We demonstrate possibility of existence of two peaks in the specific heat capacity thermal behavior.
In this work, we investigate thermodynamic properties of the one-dimensional (1D) spin-crossover molecular chain being a subject of a constant external pressure. Effective compressible degenerate Ising model is used as a theoretical framework. Using transfer matrix formalism analytic results for the low spin -- high spin crossover were obtained. We derive the exact expressions for the fraction of molecules in the high spin state, correlation function and heat capacity. We provide analysis of parameters region where the spin crossover takes place and demonstrate how pressure changes location of…
A first-order liquid-liquid phase transition in high-pressure hydrogen between molecular and atomic fluid phases has been predicted in computer simulations using ab initio molecular dynamics approaches. However, experiments indicate that molecular dissociation may occur through a continuous crossover rather than a first-order transition. Here we study the nature of molecular dissociation in fluid hydrogen using an alternative simulation technique in which electronic correlation is computed within quantum Monte Carlo, the so-called Coupled Electron Ion Monte Carlo (CEIMC) method. We find no evi…
We investigate within a self-consistent theory the molecular instabilities arising in the normal state of a homogeneous degenerate Fermi gas, covering the whole BEC-BCS crossover. These are the standard instability for molecular formation, the BCS instability which corresponds to the formation of Cooper pairs and the related Bose-Einstein instability. These instabilities manifest themselves in the properties of the particle-particle vertex, which we calculate in a ladder approximation. To find the critical temperatures corresponding to these various instabilities, we handle the properties of t…
We report the observation of a distinct correlation between the kinetic fragility index $m$ and the reduced Arrhenius crossover temperature $θ_A = T_A/T_g$ in various glass-forming liquids, identifying three distinguishable groups. In particular, for 11 glass-forming metallic liquids, we universally observe a crossover in the mean diffusion coefficient from high-temperature Arrhenius to low-temperature super-Arrhenius behavior at approximately $θ_A \approx 2$ which is in the stable liquid phases. In contrast, for fragile molecular liquids, this crossover occurs at much lower $θ_A \approx 1.4$ …
Spin-crossover has a wide range of applications from memory devices to sensors. This has to do mainly with the nature of the transition, which may be abrupt, gradual or incomplete and may also present hysteresis. This transition alters the properties of a given sample, such as magnetic moment, color and electric resistance to name some. Yet, a thorough understanding of the phenomenon is still lacking. In this work a simple model is provided to mimic some of the properties known to occur in spin-crossover. A detailed study of the model parameters is presented using a mean field approach and exh…
Photo-induced switching from the low-spin state to the high-spin state is studied in a model of spin-crossover materials, in which long-range interactions are induced by elastic distortions due to different molecular sizes the two spin states. At a threshold value of the light intensity we observe nonequilibrium critical behavior corresponding to a mean-field spinodal point. Finite-size scaling of the divergence of the relaxation time is revealed by analysis of kinetic Monte Carlo simulations.
An electronically coarse-grained model for water reveals a persistent vestige of the liquid-gas transition deep into the supercritical region. A crossover in the density dependence of the molecular dipole arises from the onset of non-percolating hydrogen bonds. The crossover points coincide with the Widom line in the scaling region but extend further, tracking the heat capacity maxima, offering evidence for liquid- and gas-like state points in a "one-phase" fluid. The effect is present even in dipole-limit models suggesting that it is common for all molecular liquids exhibiting dipole enhancem…
Understanding glasses and the glass transition requires comprehending the nature of the crossover from the ergodic (or equilibrium) regime, in which the stationary properties of the system have no history dependence, to the mysterious glass transition region, where the measured properties are non-stationary and depend on the protocol of preparation. In this work we use non-equilibrium molecular dynamics simulations to test the main features of the crossover predicted by the \emph{molecular} version of the recently-developed multicomponent non-equilibrium self-consistent generalized Langevin eq…
We consider a two-species degenerate Fermi gas coupled by a diatomic Feshbach resonance. We show that the resulting superfluid can exhibit a form of coherent BEC-to-BCS oscillations in response to a nonadiabatic change in the system's parameters, such as for example a sudden shift in the position of the Feshbach resonance. In the narrow resonance limit, the resulting soliton-like collisionless dynamics can be calculated analytically. In equilibrium the thermodynamics can be accurately computed across the full range of BCS-BEC crossover, with corrections controlled by the ratio of the resonance…
Microscopic current fluctuations are inseparable from conductance. We give an integral account of both quantized conductance and nonequilibrium thermal noise in one-dimensional ballistic wires. Our high-current noise theory opens a very different window on such systems. Central to the role of nonequilibrium ballistic noise is its direct and robust dependence on the statistics of carriers. For, with increasing density, they undergo a marked crossover from classical to strongly degenerate behavior. This is singularly evident where the two-probe conductance shows quantized steps: namely, at the d…
We consider a single vortex in a superfluid Fermi gas in the BCS-BEC crossover regime near a Feshbach resonance. The effect of the molecular Bose-Einstein condensate upon the vortex structure is discussed within the mean field approximation at zero temperature. Using the self-consistent Bogoliubov-de Gennes equation of the fermion-boson coupled model, we calculate density distributions of atoms and molecules. As the number of the molecules increases, both atomic and molecular density changes from BCS-like distribution to BEC-like. We also study the change of the vortex core size in the crossov…
We study the origin of the cooperative nature of spin crossover (SC) between low spin (LS) and high spin (HS) states from the view point of elastic interactions among molecules. As the size of each molecule changes depending on its spin state, the elastic interaction among the lattice distortions provides the cooperative interaction of the spin states. We develop a simple model of SC with intra and intermolecular potentials which accounts for the elastic interaction including the effect of the inhomogeneity of the spin states, and apply constant temperature molecular dynamics based on the Nosé…
After the discovery of the phenomena of light-induced excited spin state trapping (LIESST), the functional properties of metal complexes have been studied intensively. Among them, cooperative phenomena involving low spin-high spin (spin-crossover) transition and magnetic ordering have attracted interests, and it has become necessary to formulate a unified description of both phenomena. In this work, we propose a model in which they can be treated simultaneously by extending the Wajnflasz-Pick model including a magnetic interaction. We found that this new model is equivalent to Blume-Emery-Grif…
Pressure-induced phase transitions of spin-crossover materials were simulated by a Monte Carlo simulation in the constant pressure ensemble for the first time. Here, as the origin of the cooperative interaction, we adopt elastic interaction among the distortions of the lattice due to the difference of the molecular sizes in different spin states, i.e., the high spin (HS) state and the low spin (LS) state. We studied how the temperature dependence of the ordering process changes with the pressure, and we obtained a standard sequence of temperature dependences that has been found in changing oth…
The collective properties of spin-crossover chains are studied. Spin-crossover compounds contain ions with a low-spin ground state and low lying high-spin excited states and are of interest for molecular memory applications. Some of them naturally form one-dimensional chains. Elastic interaction and Ising exchange interaction are taken into account. The transfer-matrix approach is used to calculate the partition function, the fraction of ions in the high-spin state, the magnetization, susceptibility, etc., exactly. The high-spin-low-spin degree of freedom leads to collective effects not presen…
The thermodynamic properties of a nonrelativistic free-electron Fermi gas is of fundamental interest in condensed matter physics. Properties previously studied in three-dimensions (3D) in the low- and high-temperature limits include the internal energy, heat capacity, zero-field magnetic spin susceptibility, and pressure. Here we report solutions for the temperature dependence spanning these two temperature regimes of the chemical potential, internal energy, magnetic susceptibility, and the heat capacity at constant volume in 1D, 2D, and 3D. Also calculated are the pressure, enthalpy, heat cap…
We study a strongly interacting dense hard-sphere system confined between two parallel plates by event-driven molecular dynamics simulations to address the fundamental question of the nature of the 3D to 2D crossover. As the fluid becomes more and more confined the dynamics of the transverse and lateral degrees of freedom decouple, which is accompanied by a diverging time scale separating 2D from 3D behavior. Relying on the time-correlation function of the transversal kinetic energy the scaling behavior and its density-dependence is explored. Surprisingly, our simulations reveal that its time-…
We discuss the BCS-BEC crossover in a degenerate Fermi gas of two hyperfine states interacting close to a Feshbach resonance. This system has quasi-molecular Bosons associated with a Feshbach resonance, and this kinds of coupled Boson-Fermion model has been recently applied to Fermi atomic gases within a mean-field approximation. We show that by including fluctuation contribution to the free energy similar to that condiered by Nozi'eres and Schmitt-Rink, the character of the superfluid phase transition continuously changes from the BCS-type to the BEC-type, as the threshold of the quasi-molecu…
A hallmark of a thermodynamic phase transition is the qualitative change of system thermodynamic properties such as energy and heat capacity. On the other hand, no phase transition is thought to operate in the supercritical state of matter and, for this reason, it was believed that supercritical thermodynamic properties vary smoothly and without any qualitative changes. Here, we perform extensive molecular dynamics simulations in a wide temperature range and find that a deeply supercritical state is thermodynamically heterogeneous, as witnessed by different temperature dependence of energy, he…
In this work, we report on inelastic X-ray scattering experiments combined with the molecular dynamics simulations on deeply supercritical Ar. The presented results unveil the mechanism and regimes of sound propagation in the liquid matter and provide compelling evidence for the adiabatic-to-isothermal longitudinal sound propagation transition. We introduce a Hamiltonian predicting low-frequency transverse sound propagation gaps, which is confirmed by experimental findings and molecular dynamics calculations. As a result, a universal link is established between the positive sound dispersion (P…
Theory of current hysteresis for tunneling through a molecular quantum dot (MQD) with strong electron-vibron interactions and attractive electron-electron correlations is developed. The dot is modeled as a d-fold degenerate energy level weakly coupled to the leads. The effective attractive interaction between polarons in the dot results in a "switching" phenomenon in the current-voltage characteristics when d>2, in agreement with the results for the phenomenological negative-U model. The degenerate MQD with strong electron-vibron coupling has two stable current states in certain interval of th…
The structural properties of additive binary hard-sphere mixtures are addressed as a follow-up of a previous paper [S. Pieprzyk et al., Phys. Rev. E 101, 012117 (2020)]. The so-called rational-function approximation method and an approach combining accurate molecular dynamics simulation data, the pole structure representation of the total correlation functions, and the Ornstein-Zernike equation are considered. The density, composition, and size-ratio dependencies of the leading poles of the Fourier transforms of the total correlation functions $h_{ij} (r)$ of such mixtures are presented, those…
