Discrete nature of thermodynamics in confined ideal Fermi gases

Intrinsic discrete nature in thermodynamic properties of Fermi gases appears under strongly confined and degenerate conditions. For a rectangular confinement domain, thermodynamic properties of an ideal Fermi gas are expressed in their exact summation forms. For 1D, 2D and 3D nano domains, variations of both number of particles and internal energy per particle with chemical potential are examined. It is shown that their relation with chemical potential exhibits a discrete nature which allows them to take only some definite values. Furthermore, quasi-irregular oscillatory-like sharp peaks are observed in heat capacity. New nano devices can be developed based on these behaviors.     

Local elastic properties of nano-confined fluids: A density functional study

The understanding of mechanical properties of confined fluids is essential for modeling and manipulating of nano-scaled systems. Unlike the uniform phase, the confined fluids usually display different features in structure and related properties. Due to the presence of the confining geometry, the density profile and many physical and chemical properties may be position-dependent. The aim of our research is to derive an expression for the local elastic property by using the classical elastic theory. Both the bulk and shear moduli are expressed as functional of density of particle. The theoretical result derived is applied to the Lennard-Jones fluids confined in nano-cavity. Comparison of our numerical result and the simulation result is made and qualitative agreement is observed. Further, influence of bulk density, temperature and external potential on moduli is calculated and the physical mechanism is analyzed. Relationship between contact modulus and the interfacial tension is also calculated. Their opposite trend with temperature is observed.     

受限于对称性破缺狭缝间氢键流体的相平衡研究

利用密度泛函理论并结合改进的基本度量理论研究了受限于对称性破缺狭缝间氢键流体的相平衡. 首先根据氢键流体的吸附-脱附等温线及相应巨势获得不同条件下氢键流体的相图. 进一步讨论了氢键作用、狭缝间距、狭缝与流体分子间相互作用及对称性破缺程度等因素对氢键流体相平衡的影响. 结果表明, 由于狭缝与流体分子及流体分子间的相互作用存在竞争, 使得受限于对称性破缺条件下的氢键流体呈现更为复杂的相态特征.     

Oscillatory structure of confined fluids

The confinement of fluids in pores and wedges is associated with exponentially damped oscillatory packing structure, as observed with the surface forces apparatus. This paper reviews the statistical mechanics of confined fluids and then illustrates the results with density functional data for hard-sphere solvent. The free energy of the pore fluid and its functional derivatives with respect to thermodynamic fields all oscillate, as a function of pore width, with a wavelength close to the solvent diameter. In contrast, the density at the centre of pores oscillates with twice this wavelength, as a function of pore width. The development of a unified physics of confined fluids is considered. Approximations based on one-dimensional physics do extraordinarily well in planar symmetry at three-dimensions.     

The phase behaviour of a fluid in a slitlike pore with permeable walls

The confinement of a lattice fluid in a set of slitlike pores separated by semipermeable walls with a finite width has been studied. The walls are modelled by a square-well repulsive potential with a finite height. The thermodynamic properties and the phase behaviour of the system are evaluated by means of Monte Carlo simulations. For some states theoretical calculations have been made using a mean-field-type theory. These investigations confirm previous findings for confined Lennard-Jones fluids, obtained from a density functional approach. For intermediate and low potential barriers that separate the pores, the isotherms exhibit two hysteresis loops and the liquid-vapour coexistence curve divides into two branches describing condensation inside the pore and inside the permeable wall. These two branches are separated by a triple point. At temperatures lower than the triple point temperature, the condensation takes place instantaneously in both the pore and inside the permeable wall. It was found that when the temperature is scaled by the bulk critical temperature, the phase diagram emerging from this simple mean-field treatment is close to the phase diagram obtained from simulation.     

Adsorption isotherm of a Lennard-Jones nitrogen in a carbon slitlike pore

A density functional perturbation approximation based both on second-order perturbation theory and on the pore average density has been proposed to study the adsorption hysteresis of nitrogen in a carbon slit pore. The main advantage of the present approximation is that it is computationally much simpler than the original density functional approximation based on the second-order perturbation theory of liquids, and can be applied to several model fluids confined in a strong external field in order to study their structural and thermodynamic properties. The calculated adsorption hysteresis for the confined Lennard-Jones nitrogen is in very good agreement with computer simulation, even if its accuracy slightly deteriorates for the desorption branch. The calculated equilibrium particle density distributions also compare well with computer simulations, and are better than those of a density functional theory based on the so-called mean-field approximation.     

Structure of liquid-vapor interface of square well fluid confined in a cylindrical pore

By means of the canonical Monte Carlo simulations, the vapor-liquid (VL) equilibrium and structure of square well (SW) fluids confined in a single cylindrical pore with repulsive surface, have been studied. Coexistence curves of the confined VL interface are determined for a wide range of temperatures and pore diameters. It is demonstrated that the confinement not only reduces the VL coexistence region but also induces strong inhomogeneities of the VL interface: coexistence liquid densities are different at the pore center and at the wall surface. It may be considered as a preliminary step for an isolated droplet formation inside the pore, as well as a tentative reason of the two VL phase transitions of simple fluids adsorbed into disordered porous media.     

Finite-size effects in a D-dimensional ideal Fermi gas

By using the Euler-MacLaurin formula,this paper studies the thermodynamic properties of an ideal Fermi gas confined in a D-dimensional rectangular container.The general expressions of the thermodynamic quantities with the finite-size corrections are given explicitly and the effects of the size and shape of the container on the properties of the system are discussed.It is shown that the corrections of the thermodynamic quantities due to the finite-size effects are significant to be considered for the case of strong degeneracy but negligible for the case of weak degeneracy or non-degeneracy.It is important to find that some familiar conclusions under the thermodynamic limit are no longer valid for the finite-size systems and there are some novel characteristics resulting from the finite-size effects,such as the nonextensivity of the system,the anisotropy of the pressure,and so on.     

Phase transitions of fluids confined in porous silicon: A differential calorimetry investigation

The phase transitions of non-polar organic fluids and of water, confined in the pores of porous silicon samples, were investigated by Differential Scanning Calorimetry (DSC). Two types of PS samples (p^- and p⁺ type) with different pore size and morphology were used (with spherical pores with a radius of about 1.5 nm and cylindrical shape with a radius of about 4 nm respectively). The DSC results clearly show that the smaller the pores are, the larger is the decrease in the transition temperature. Moreover, a larger hysteresis between melting and freezing is observed for p⁺ type than for p^- type samples. A critical review of the thermodynamical properties of small particles and confined fluids is presented and used to interpret and discuss our DSC results. The effects of the chemical dissolution as well as the influence of anodization time are presented, showing that thick p⁺ type porous silicon layers are non-homogeneous. The DSC technique which was used for the first time to investigate fluids confined in porous silicon, enables us to deduce original information, such as the pore size distribution, the decrease in the freezing temperature of confined water, and the thickness of non-freezing liquid layer at the pore wall surface. Received: 11 May 1998 / Revised and Accepted: 29 July 1998     

Magnetic susceptibility of noninteracting fermions in a confined geometry

A model system of an ideal gas of neutral fermions in a confined geometry of different symmetry and size is theoretically examined. The behavior of these systems is found to exhibit qualitatively new features such as the oscillations in magnetic susceptibility with changing geometry size and particle density, indicating that the geometric confinement substantially affects the thermodynamic properties of the system.     

波纹误差对同轴布拉格结构反射特性的影响

利用模式匹配法建立了分析波纹参数具有随机误差的矩形槽同轴布拉格结构反射特性的理论模型,并以一个以基模(TEM)工作于220GHz附近的矩形槽同轴布拉格结构为例,研究了矩形凹槽的深度、宽度、周期长度以及位置的随机误差对其反射率频率响应的影响。数值模拟结果表明:在给定的误差范围条件下,凹槽宽度与位置的随机误差对该结构的反射性能影响较小,而凹槽深度与周期长度的随机误差是影响结构反射特性的主要因素,因此在结构的加工制备过程中应视器件性能要求严格控制两者的制造公差。     

Effects of a finite number of particles on the thermodynamic properties of a harmonically trapped ideal charged Bose gas in a constant magnetic field

We investigate the thermodynamic properties of an ideal charged Bose gas confined in an anisotropic harmonic potential and a constant magnetic field. Using an accurate density of states, we calculate analytically the thermodynamic potential and consequently various intriguing thermodynamic properties, including the Bose–Einstein transition temperature, the specific heat, magnetization, and the corrections to these quantities due to the finite number of particles are also given explicitly. In contrast to the infinite number of particles scenarios, we show that those thermodynamic properties,particularly the Bose–Einstein transition temperature depends upon the strength of the magnetic field due to the finiteness of the particle numbers, and the collective effects of a finite number of particles become larger when the particle number decreases. Moreover, the magnetization varies with the temperature due to the finiteness of the particle number while it keeps invariant in the thermodynamic limit N →∞.     

Restricted diffusion and exchange of water in porous media: average structure determination and size distribution resolved from the effect of local field gradients on the proton NMR spectrum

NMR Pulsed field gradient measurements of the restrained diffusion of confined fluids constitute an efficient method to probe the local geometry in porous media. In most practical cases, the diffusion decay, when limited to its principal part, can be considered as Gaussian leading to an apparent diffusion coefficient. The evolution of the latter as a function of the diffusion interval yields average information on the surface/volume ratio of porosities and on the tortuosity of the network. In this paper, we investigate porous model systems of packed spheres (polystyrene and glass) with known mean diameter and polydispersity, and, in addition, a real porous polystyrene material. Applying an Inverse Laplace Transformation in the second dimension reveals an evolution of the apparent diffusion coefficient as a function of the resonance frequency. This evolution is related to a similar evolution of the transverse relaxation time T2. These results clearly show that each resonance frequency in the water proton spectrum corresponds to a particular magnetic environment produced by a given pore geometry in the porous media. This is due to the presence of local field gradients induced by magnetic susceptibility differences at the liquid/solid interface and to slow exchange rates between different pores as compared to the frequency differences in the spectrum. This interpretation is nicely confirmed by a series of two-dimensional exchange experiments.     

Generalized isobaric–isothermal ensemble: application to capillary condensation and cavitation in heterogeneous nanopores

The influence of pore size and chemical heterogeneity on the adsorption/desorption hysteresis loop of a Lennard–Jones fluid confined within simple models of heterogeneous cylindrical nanopores is investigated. The thermodynamic pressure, or grand potential density, is calculated by a new method which was previously developed for mesopores (a few nanometers) to allow the introduction of chemical heterogeneity and further improved in this work for micropores (down to molecular diameters). The efficiency of the algorithm is first verified on simple cases. Secondly, we focus on the pore size effect. It is shown to have a weak influence on the capillary condensation phenomenon which always occurs around the same value of the thermodynamic pressure. On the other hand, the desorption pressure (corresponding to the liquid fracture or cavitation threshold) exhibits a linear dependence on the inverse pore radius. Finally, the effect of chemical heterogeneity, which is characterized by the relative amplitude (<40%) and wavelength (<4?nm), is investigated. It is shown to strongly influence the desorption branch of the hysteresis loop. As expected, liquid fracture is favoured by large amplitude heterogeneity. However, for a given amplitude, atomic-scale heterogeneity has a minor influence, whereas the longest wavelengths considered (4?nm) destabilize the confined liquid. It is proposed to correlate this with the typical size of the bubble critical nucleus.     

The geometric potential of a double-frequency corrugated surface

For an electron confined to a surface reconstructed by double-frequency corrugations, we give the effective Hamiltonian by the formula of geometric influences, obtain an additive scalar potential induced by curvature that consists of attractive wells with different depth. The difference is generated by the multiple frequency of the double-frequency corrugation. Subsequently, we investigate the effects of geometric potential on the transmission probability, and find the resonant tunneling peaks becoming rapidly sharper and the transmission gaps being substantially widened with increasing the multiple frequency. As a potential application, double-frequency corrugations can be employed to select electrons with particular incident energy, as an electronic switch, which are more effective than a single-frequency ones.     

Absence of simulation evidence for critical depletion in slit pores

Recent Monte Carlo simulation studies of a Lennard-Jones fluid confined to a mesoscopic slit pore have reported evidence of "critical depletion" in the pore local number density near the liquid-vapor critical point. In this Brief Report we demonstrate that the observed depletion effect is in fact a simulation artifact arising from small systematic errors associated with the use of long range corrections for the potential truncation. Owing to the large near-critical compressibility, these errors lead to significant changes in the pore local number density. We suggest ways of avoiding similar problems in future studies of confined fluids.     

Molecular simulation study of triangle-well fluids confined in slit pores

Grand canonical Monte Carlo simulations are used to study the behaviour of triangle-well (TW) fluids with variable well widths confined inside slit pores. The effect of individual factors influencing the properties of confined fluids such as fluid–fluid interactions, pore size and pore wall–fluid interactions are obtained using simulations as it is difficult to experimentally determine the same. An interesting observation of this study is that inside the narrow pore of slit height h* = 5 at the high-pressure condition of P* = 0.8, for the TW fluid with long-range attraction or for the fluid at a low temperature for even a short-range attraction, the density profiles show layering such that there is a sticking tendency of the particles at centre, while there is a depletion of particles near the wall (as the layers at the centre have higher density peak heights than near the walls).     

Effect of shape factor on the electrokinetic response of slot-like capillaries

The effect of the shape factor on the electrokinetic response of pressure-driven liquid flow through slot-like capillaries is analyzed in this work. The electrokinetic response is found by first solving for the electrical potential using the Poisson–Boltzmann equation, and then using it as an input to construct an external force term in the Navier–Stokes equation. It is found that flow properties are significantly modified for small pore sizes with hydraulic radius in the range of microns and submicrons, according to the properties of the electrolyte solution. The modified flow rate in the presence of such electrokinetic effects can be less than 50% of the predictions expected with conventional flow models such as Darcy's equation. Apparent viscosities larger than expected are calculated using the reduced flow. Actual values are dependent on the capillary dimensions, pressure gradient, solid-surface conductivity, and properties of the electrolyte fluid. For a rectangular capillary cross-sectional geometry the apparent viscosity and friction coefficients values decrease with the shape factor in a nontrivial way. These results are relevant for the modelling of certain porous formations of interest to the oil industry.