The Kirkwood-Buff theory is a cornerstone of the statistical mechanics of liquids and solutions. It relates volume integrals over the radial distribution function, so-called Kirkwood-Buff integrals (KBIs), to particle number fluctuations and thereby to various macroscopic thermodynamic quantities such as the isothermal compressibility and partial molar volumes. Recently, the field has seen a strong revival with breakthroughs in the numerical computation of KBIs and applications to complex systems such as bio-molecules. One of the main emergent results is the possibility to use the finite volume KBIs as a tool to access finite volume thermodynamic quantities. The purpose of this Perspective is to shed new light on the latest developments and discuss future avenues.

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It is known that thermodynamic properties of a system change upon confinement. To know how, is important for modelling of porous media. We propose to use Hill’s systematic thermodynamic analysis of confined systems to describe two-phase equilibrium in a nanopore. The integral pressure, as defined by the compression energy of a small volume, is then central. We show that the integral pressure is constant along a slit pore with a liquid and vapor in equilibrium, when Young and Young–Laplace’s laws apply. The integral pressure of a bulk fluid in a slit pore at mechanical equilibrium can be understood as the average tangential pressure inside the pore. The pressure at mechanical equilibrium, now named differential pressure, is the average of the trace of the mechanical pressure tensor divided by three as before. Using molecular dynamics simulations, we computed the integral and differential pressures, ̂p and p, respectively, analysing the data with a growing-core methodology. The value of the bulk pressure was confirmed by Gibbs ensemble Monte Carlo simulations. The pressure difference times the volume, V, is the subdivision potential of Hill, (p − ̂p)V = ɛ. The combined simulation results confirm that the integral pressure is constant along the pore, and that ɛ/V scales with the inverse pore width. This scaling law will be useful for prediction of thermodynamic properties of confined systems in more complicated geometries.

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The accurate description of the behavior of fluids in nanoporous materials is of great importance for numerous industrial applications. Recently, a new approach was reported to calculate the pressure of nanoconfined fluids. In this approach, two different pressures are defined to take into account the smallness of the system: the so-called differential and the integral pressures. Here, the effect of several factors contributing to the confinement of fluids in nanopores are investigated using the definitions of the differential and integral pressures. Monte Carlo (MC) simulations are performed in a variation of the Gibbs ensemble to study the effect of the pore geometry, fluid-wall interactions, and differential pressure of the bulk fluid phase. It is shown that the differential and integral pressure are different for small pores and become equal as the pore size increases. The ratio of the driving forces for mass transport in the bulk and in the confined fluid is also studied. It is found that, for small pore sizes (i.e., < 5σfluid ), the ratio of the two driving forces considerably deviates from 1. @en

Molecular Monte Carlo simulations are used to compute the three-phase (hydrate-liquid water-gas) equilibrium lines of methane and carbon dioxide hydrates, using the Transferable Potentials for Phase Equilibria model for carbon dioxide, the united atom optimized potential for liquid simulations model for methane, and the TIP4P/Ice and TIP4P/2005 models for water. The three-phase equilibrium temperatures have been computed for pressures between 50 and 4000 bar via free-energy calculations. The computed results are as expected for methane hydrates but deviate from the direct-coexistence molecular dynamics (MD) studies for carbon dioxide hydrates. At pressures higher than 1000 bar, both the methane and carbon dioxide hydrates dissociate at lower temperatures than expected from experiments and MD studies. The dissociation enthalpy is found to be largely independent on water models, and its values are measured to be 7.6 and 6.0 kJ/mol of water for methane hydrates and carbon dioxide hydrates, respectively. We evaluate the effect of systematic errors on the determination of chemical potentials and show that systematic errors of 0.1 kJ/mol in the chemical potential of water correspond to deviations of 5 K in the three-phase equilibrium temperatures. (Graph Presented).

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A sound knowledge of thermodynamic properties of sII hydrates is of great importance to understand the stability of sII gas hydrates in petroleum pipelines and in natural settings. Here, we report direct molecular dynamics (MD) simulations of the thermal expansion coefficient, the compressibility, and the specific heat capacity of C₃H₈, or tetrahydrofuran (THF), in mixtures of CH₄ or CO₂, in sII hydrates under a wide, relevant range of pressure and temperature conditions. The simulations were started with guest molecules positioned at the cage center of the hydrate. Annealing simulations were additionally performed for hydrates with THF. For the isobaric thermal expansion coefficient, an effective correction method was used to modify the lattice parameters, and the corrected lattice parameters were subsequently used to obtain thermal expansion coefficients in good agreement with experimental measurements. The simulations indicated that the isothermal expansion coefficient and the specific heat capacity of C₃H₈-pure hydrates were comparable but slightly larger than those of THF-pure hydrates, which could form Bjerrum defects. The considerable variation in the compressibility between the two appeared to be due to crystallographic defects. However, when a second guest molecule occupied the small cages of the THF hydrate, the deviation was smaller, because the subtle guest-guest interactions can offset an unfavorable configuration of unstable THF hydrates, caused by local defects in free energy. Unlike the methane molecule, the carbon dioxide molecule, when filling the small cage, can increase the expansion coefficient and compressibility as well as decrease the heat capacity of the binary hydrate, similar to the case of sI hydrates. The calculated bulk modulus for C₃H₈-pure and binary hydrates with CH₄ or CO₂ molecule varied between 8.7 and 10.6 GPa at 287.15K between 10 and 100 MPa. The results for the specific heat capacities varied from 3155 to 3750.0 J kg^-1 K^-1 for C₃H₈-pure and binary hydrates with CH₄ or CO₂ at 287.15K. These results are the first of this kind reported so far. The simulations show that the thermodynamic properties of hydrates largely depend on the enclathrated compounds. This provides a much-needed atomistic characterization of the sII hydrate properties and gives an essential input for large-scale discoveries of hydrates and processing as a potential energy source.

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Using the analogue of the electric inductance, we reveal the properties of the thermal inductance in GaN-based light-emitting diode devices by testing their transient thermal behaviors. We find that the devices exhibit a transient thermal response under step-down or step-up currents and observe notable inductive phenomena of the temperature response as time evolves from start up to some hundred microseconds. We define thermal inductance as the rapid change in device temperature that is opposite to the temperature change expected from the power input. These findings can promote new temperature measurements, and novel thermal analyses of high-frequency semiconductor devices that combining the thermal resistances, thermal capacitances, and thermal inductances.@en