Second-order Perturbation Density Functional Theory Research Articles

Effect of critical fluctuations on adsorption of van der Waals fluid in a spherical cavity

A recently proposed non-uniform fifth-order thermodynamic perturbation theory (TPT) is employed to investigate the adsorption of a hard core attractive Yukawa (HCAY) fluid in a spherical cavity. Extensive comparison with available simulation data indicate that the non-uniform fifth-order TPT is sufficiently reliable in calculating the density profiles of the HCAY fluid in the highly confining geometry, and generally is more accurate than a previous third-order + second-order perturbation density functional theory. The non-uniform fifth-order TPT is free from numerically solving an Ornstein–Zernike integral equation, and also free of any adjustable parameter; consequently, it can be applied to both supercritical and subcritical temperature regions. The non-uniform fifth-order TPT is employed to investigate critical adsorption of the HCYA fluid in a single spherical cavity – it is disclosed that the critical fluctuations near the critical point induce depletion adsorption – quantitative theoretical calculation on relationship between the critical depletion adsorption, parameters of coexistence bulk phase and the responsible external field is in agreement with qualitative physical analysis.

Going beyond the mean field approximation in classical density functional theory andapplication to one attractive core-softened model fluid

A novel scheme is advanced for an excess Helmholtz free energy density functional. Thepresent scheme is isomorphic to one frequently used mean field approximation (MFA)methodology, but goes beyond the latter in that the present scheme contains a bulksecond-order direct correlation function (DCF) which can be obtained by numericallysolving a bulk Ornstein–Zernike (OZ) integral equation theory (IET), and is therefore ingeneral more accurate than the bulk second-order DCF expected from MFA methodology.The scheme is applied in the framework of classical density functional theory (DFT) toone so-called attractive core-softened model potential with a double square wellattraction in homogeneous conditions. Quantitatively it is found that the presentscheme is in general more accurate than two previously confirmed third-order + second-order perturbation DFT and non-uniform fifth-order thermodynamic perturbation theory,even if the present scheme is implemented in a purely predictive manner and the third-order + second-order perturbation DFT is implemented in a partially predictive manner. Qualitatively thepresent scheme is characterized by several desirable features not possessed by previousmethodologies: (i) It is not concerned with any adjustable parameters, and this allows forhandy applications. (ii) It does not deal with problems of determining self-consistently bothan effective hard sphere diameter and a tail contribution to the full pair potentialunder consideration. (iii) Although the present scheme uses OZ IET to supplyinput information, it is safely applicable to subcritical regions of the bulk phasediagram.

New free energy density functional and application to core-softened fluid

A new free energy density functional is advanced for general nonhard sphere potentials characterized by a repulsive core with a singular point at zero separation. The present functional is characterized by several features. (i) It does not involve with dividing the potentials into hard-sphere-like contribution and tail contribution in sharp contrast with usual effective hard sphere model+mean field approximation for tail contribution. (ii) It has no recourse to the use of weighted density and is computationally modest; it also does not resort to an equation of state and/or an excess Helmholtz free energy of bulk fluid over a range of density as input. Consequently, all of input information can be obtained by numerical solution of a bulk Ornstein-Zernike integral equation theory (OZ IET). Correspondingly, despite the use of bulk second-order direct correlation function (DCF) as input, the functional is applicable to the subcritical region. (iii) There is no any adjustable parameter associated with the present functional, and an effective hard sphere diameter entering the functional can be determined self-consistently and analytically once the input information, i.e., the second-order DCF and pressure of the coexistence bulk fluid, are obtained by the OZ IET. The present functional is applied to a core-softened fluid subject to varying external fields, and the density distributions predicted by the present functional are more self-consistent with available simulation results than a previous third-order+second-order perturbation density functional theory.

Structural Properties of a Model System with Effective Interparticle Interaction Potential Applicable in Modeling of Complex Fluids

We report grand canonical ensemble Monte Carlo (MC) simulation and theoretical studies of the structural properties of a model system described by an effective interparticle interaction potential, which incorporates basic interaction terms used in modeling of various complex fluids composed of mesoscopic particles dispersed in a solvent bath. The MC results for the bulk radial distribution function are employed to test the validity of the hard-sphere bridge function in combination with a modified hypernetted chain approximation (MHNC) in closing the Ornstein-Zernike (OZ) integral equation, while the MC data for the density profiles in different inhomogeneous environments are used to assess the validity of the third-order+second-order perturbation density functional theory (DFT). We found satisfactory agreement between the results predicted by the pure theories and simulation data, which classifies the proposed theoretical approaches as convenient tools for the investigation of complex fluids. The present investigation indicates that the bridge function approximation and density functional approximation, which are traditionally used for the study of neutral atomic fluids, also perform well for complex fluids only on condition that the underlying effective potentials include a highly repulsive core as an ingredient.

Fifth-order thermodynamic perturbation theory of uniform and nonuniform fluids

A recently proposed numerical third-order thermodynamic perturbation theory (TPT) is extended to its fifth-order counterpart. Extensive performance evaluation based on several model potentials indicates that the fifth-order version is generally superior to both the third-order version and a well-known second-order macroscopic compressibility approximation TPT, and is at least comparable to an accurate self-consistent Ornstein-Zernike integral equation approximation (SCOZA) with regard to predictions of varying bulk thermodynamic properties. A bulk second-order direct correlation function (DCF) free of numerical solution of a bulk OZ integral equation, is proposed, which, in combination with the framework of classical density functional theory (DFT) and a thermodynamic consistency condition, extends the uniform fifth-order TPT to nonuniform case. Grand canonical ensemble Monte Carlo simulation is carried out to produce density profile of a core-softened fluid confined in a hard spherical cavity, the resultant density profile is employed to evaluate the performance of the present nonuniform fifth-order TPT and a recently proposed third +second-order perturbation DFT. It is found that the present nonuniform fifth-order TPT is generally more accurate than the third+second-order perturbation DFT. Additional advantages of the present nonuniform fifth-order TPT over the third +second-order perturbation DFT is discussed.