Sharif Digital Repository

We present in this paper a new method of modifying hard-core potentials to correctly predict the equilibrium and non-equilibrium properties of real fluids at low densities (specifically when ρ ≤ B/C where ρ is density, and B and C are the second and third virial coefficients) only by one set of potential parameters. Because the molecular diameter becomes smaller when temperature increases, we introduced a new expression for the variation of molecular diameter with temperature that incorporates this effect. The temperature dependence of the diameter was used in both Sutherland (ST) and square-well (SW) potential models to modify the second virial coefficient. Then we have shown that the... 

Metallic nanoparticles are interesting because of their use in catalysis and sensors. The surface energy of the FCC platinum nanoparticles are investigated via molecular dynamics simulation using Quantum Sutton-Chen (QSC) potential. We have calculated the Gibbs free energy for the FCC platinum bulk and also for its nanoparticle. All calculations have been carried out at zero pressure. We have used the thermodynamic integration method to obtain the Gibbs free energy. The total Gibbs free energy is taken as the sum of its central bulk and its surface free energy. We have calculated the free energy of a platinum nanoparticle as a function of temperature  

As the delay time and hence nuclei formation play a crucial role in the pathophysiology of sickle cell disease, MD simulation and molecular mechanics-Poisson-Boltzmann surface area (MM-PBSA) calculations have been performed on three systems of hemoglobin; namely dimer of hemoglobin with valine (Hb S), tryptophan (Hbβ6W), and phenylalanine (Hbβ6F) at β6 position. The structural changes due to these aromatic substitutions are investigated. It is shown that β subunits have significant impact on the differences between a dimer and other crystal structures. Transition from a dimer to polymer for Hb S system affects the donor molecule more than that of the acceptor. In the case of donor and... 

Molecular dynamics, MD, simulation of calcite (CaCO3) is selected to compare the p-v-T behaviour of some universal equations of state, UEOS, for the temperature range 100 K ≤ T 800 ≤ K, and pressures up to 3000 kbar. The isothermal sets of p-v-T data generated by simulation were each fitted onto some three- and two-parameter EOSs including Parsafar and Mason (PM), Linear Isotherm Regularity (LIR), Birch-Murnaghan (BM), Shanker, Vinet, Baonza and Modified generalized Lennard-Jones (MGLJ) EOSs. It is found that the MD data satisfactorily fit these UEOS with reasonable precision. Some features for a good UEOS criteria such as temperature dependencies of coefficients, pressure deviation,... 

A numerical method based on the transfer matrix method is developed to calculate the critical temperature of two-layer Ising ferromagnet with a weak inter-layer coupling. The reduced internal energy per site has been accurately calculated for symmetric ferromagnetic case, with the nearest neighbor coupling K1 = K2 = K (where K1 and K2 are the nearest neighbor interaction in the first and second layers, respectively) with inter-layer coupling J. The critical temperature as a function of the inter-layer coupling ξ = J/K, is obtained for very weak inter-layer interactions, ξ < 0.1. Also a different function is given for the case of the strong inter-layer interactions (ξ > 1). The importance of... 

Ising models in nanosystems are studied in the presence of a magnetic field. For a one-dimensional (1-D) array of spins interacting via nearest-neighbour and next-nearest-neighbour interactions we calculate the heat capacity, the surface energy, the finite-size free energy and the bulk free energy per site. The heat capacity versus temperature exhibits a common wide peak for systems of any size. A small peak also appears at lower temperatures for small arrays when the ratio of magnetic field spin interaction energy over the nearest-neighbour spin-spin interaction energy, f, is within 0 < F ≤ 0.10 . The peak becomes smaller for longer array and eventually vanishes for long arrays,... 

In the present work, several new thermodynamic linear isotherm regularities for the dense fluids have been derived for the first time. For this purpose, the thermodynamic perturbation theory (TPT) employing only the attractive effective pair potential (AEPP) as u(r) = - ϵeff (σeff / r)m was used, where σeff which is the effective hard core diameter, is temperature dependent and m > 0. Based on the derived regularities, the isotherm (Z - Z(0))v2 is a linear function of ρ2, ρ and 1/ρ, depends on the values of m = 12, 9 and 6, respectively where Z - Z(0) is the difference between the experimental compressibility factor of the real fluid (Z) and that of the reference fluid (Z(0)). Also, Z - Z(0)... 

In the present work, the thermodynamic of dense fluids, both compressed liquids and dense supercritical fluids, has been modeled, solely, based on the contribution of attraction of effective pair potential. The intermolecular interaction is modeled by the hard-core Yukawa potential (HCY) as an effective pair potential (EPP) with temperature dependent hard-core diameter. Using this EPP in the exact thermodynamic relations, an equation of state (EoS) for the compressibility factor of dense fluid has been derived. This EoS shows that (Z - ZCS) as function of ρ1/3 must be linear for each isotherm of fluid where ZCS is the compressibility factor of the reference fluid (Carnahan-Starling (CS) EoS)... 

We present an approach for constant-pressure molecular dynamics simulations. This approach is especially designed for finite systems, for which no periodic boundary condition applies. A molecular dynamics (MD) simulation for Ni nanoclusters is used to calculate their pressurevolumetemperature (pvT) data for the temperature range 200 K≤T≤400 K, and pressures up to 600 kbar. Isothermal sets of pvT data were generated by the simulation; each set was fitted by three equations of state (EoSs): Linear Isotherm Regularity-II (LIRII), BirchMurnaghan (BM), and EOS III. It is found that the MD data are satisfactorily reproduced by the EoSs with reasonable precision. Some features of the EoSs criteria,... 

The formation and diffusion of a vacancy in a silver nanocluster are studied via a combination of first-principles and statistical mechanics simulations. A 38-atom truncated-octahedral (TO) arrangement and its homologue with 37 Ag atoms and one vacancy are considered, and density-functional calculations are performed to derive the energies of the local minima and the energy barriers connecting them. These data are then used as an input for a study of the system dynamics via a kinetic Monte Carlo algorithm, evaluating site occupancies, diffusion coefficient and equilibration time. It is found that vacancy formation and diffusion represents a viable path for atom-atom exchange in these... 

In this study, adsorption of important pollutant cations on the surface of graphitic carbon nitride (g-C3N4) was investigated by density functional theory. The calculations indicated that N6 cavity surrounded by triazine units is the most probable adsorption site on this surface. The structural optimizations also predicted a planar surface for Cr3+, and Ni2+/g-C3N4 systems while the structure of the surface for other systems indicated a considerable distortion with strong dependency on the cation size. Also, g-C3N4 surface exhibited the high adsorption energies for Cr3+, As3+, and Sb3+ ions in the gas phase. However, formation energies of the metal-aquo complexes of these cations indicated... 

Two new correlation functions with three adjustable parameters for the calculation of thermal conductivity of gases, liquids, and refrigerants over wide temperature-pressure ranges are presented. It is shown that by using suitable mathematical expressions for the correlation functions, the number of adjustable parameters can be limited to three, which is less than for similar functions. The average and maximum deviation of the correlation compared with the measured data is about 1% and 8%, respectively  

The energetics and kinetic energy barriers of vacancy/atom exchange in a 37-atom truncated octahedron Ag-Pt binary cluster in the Ag-rich range of compositions are investigated via a first-principles atomistic approach. The energy of the local minima obtained considering various distributions of a single vacancy and a few Pt atoms within the cluster and the energy barriers connecting them are evaluated using accurate density-functional calculations. The effects of the simultaneous presence of a vacancy and Pt atoms are found to be simply additive when their distances are larger than first-neighbors, whereas when they can be stabilizing at low Pt content due to the release of strain by the... 

In this work, a new method based on the modified Enskog theory (MET) is presented for calculation of transport properties at high densities (ρ > ρc). The main limitation of using the MET is lack of experimental data for co-volume, b0. We have substituted b0 from hard sphere (HS) theory and zero density transport properties from the kinetic theory of gases for HS in the MET expression, because of the fact that dense fluids behave more and less like a HS fluid. As a result, a simple linear expression for the self diffusion (D) and quadratic expressions for viscosity (η) and thermal conductivity (λ) coefficients have been obtained in terms of Y at high densities (ρ > ρc), where Y = (T (∂ p / ∂... 

Recently, a new potential model has been proposed for the intermolecular interactions of model pure fluids and it was shown that the derived Equation Of State (EOS), based on this potential, can properly predict the thermodynamic properties of these.fluids. In addition to simplicity and, to some extent, the realistic form, this potential has a parameter (α) which controls the range of the attraction tail. In the first part of this study, the proposed potential and derived EOS are extended to binary mixtures of model fluids. In a similar manner to that of the pure fluids, the results obtained are consistent with the data available from simulation studies. In the second part, after... 

Different equations of state (EOSs) have been used to obtain analytical expressions for the ideal curves, namely, the Joule-Thomson inversion curve (JTIC), Boyle curve (BC), and Joule inversion curve (JIC). The selected EOSs are the Redlich-Kwong (RK), Soave-Redlich-Kwong (SRK), Deiters, linear isotherm regularity (LIR), modified LIR (MLIR), dense system equation of state (DSEOS), and van der Waals (vdW). Analytical expressions have been obtained for the JTIC and BC only by using the LIR, MLIR, and vdW equations of state. The expression obtained using the LIR is the simplest. The experimental data for the JTIC and the calculated points from the empirical EOSs for the BC are well fitted into... 

A new hard-core potential model was recently used to calculate thermodynamic properties of some model fluids, including equilibrium properties, such as compressibility factor and internal energy. A Lennard-Jones (LJ) like potential has been used to modify the repulsive part of the potential. The modified potential contains five parameters, namely, R, and HS. The parameter is the tail of the attractive branch whose value changes from zero to one. In this work, we have chosen = 1 to make the potential continuous at separation r = R, where the parameter R is the well width. R lies in the range 1.2 to 2.5, and R = 1.3 was found to be the best value for all real gases studied. The parameter is... 

An analytical expression for the fugacity coefficient of supercritical fluids has been derived from the equation of state. Here, the equation of state known as the linear isotherm regularity, LIR, is used to obtain this expression. We have inverted the LIR equation of state to obtain an appropriate expression for fugacity calculation. The inverted LIR (ILIR) works well at high pressures; but at high temperatures, Tr = T/Tc ≥2, ILIR is valid for the entire pressure range. ILIR is valid over a wide temperature range. Unlike LIR, ILIR is also valid at temperatures above twice the Boyle temperature. Like LIR, the inverted equation is a general equation of state which is valid for all types of... 

In this work, the group contribution approach has been used in combination with the linear isotherm regularity (LIR) equation of state to estimate pvT properties of primary, secondary and tertiary alcohols, ketones and 1-carboxylic acid. In addition, the isothermal compressibility and thermal expansion coefficient of these compounds have been predicted. We assume each of these organic compounds as a hypothetical mixture of methyl, methylene and a functional group, in which the interaction potential of each pair is assumed to be the average effective pair potential. Then, the LIR equation of state (EOS) has been extended to such a hypothetical mixture. Three basic compounds, namely propane,... 

Regularities shown by different fluids along the contour of the ideal compressibility factor Z= PV/(RT)=1 in the temperature density plane was used to test the accuracy of the equations of state and derive temperature dependencies of their parameters. The contour, also known as the Zeno line, was empirically observed to be nearly linear. The precision of the van der Waals equation in predicting the Zeno line was evaluated. It was shown that the equation could predict a linear relation between temperature and density on the Z=1 contour, qualitatively