Improved analytic longitudinal response analysis for axisymmetric launch vehicles. Volume I - Linear analytic model

Improved analytic longitudinal response analysis for axisymmetric launch vehicles - linear mode

Asymptotic decay of pair correlations in a Yukawa fluid

We analyse the $r \to \infty$ asymptotic decay of the total correlation function, $h(r)$, for a fluid composed of particles interacting via a (point) Yukawa pair potential. Such a potential provides a simple model for dusty plasmas. The asymptotic decay is determined by the poles of the liquid structure factor in the complex plane. We use the hypernetted-chain closure to the Ornstein-Zernike equation to determine the line in the phase diagram, well-removed from the freezing transition line, where crossover occurs in the ultimate decay of $h(r)$, from monotonic to damped oscillatory. We show: i) crossover takes place via the same mechanism (coalescence of imaginary poles) as in the classical one-component plasma and in other models of Coulomb fluids and ii) leading-order pole contributions provide an accurate description of $h(r)$ at intermediate distances $r$ as well as at long range.Comment: 5 pages, 3 figure

Solvent fluctuations around solvophobic, solvophilic and patchy nanostructures and the accompanying solvent mediated interactions

Using classical density functional theory (DFT) we calculate the density profile $\rho({\mathbf r})$ and local compressibility $\chi({\mathbf r})$ of a simple liquid solvent in which a pair of blocks with (microscopic) rectangular cross-section are immersed. We consider blocks that are solvophobic, solvophilic and also ones that have both solvophobic and solvophilic patches. Large values of $\chi({\mathbf r})$ correspond to regions in space where the liquid density is fluctuating most strongly. We seek to elucidate how enhanced density fluctuations correlate with the solvent mediated force between the blocks, as the distance between the blocks and the chemical potential of the liquid reservoir vary. For sufficiently solvophobic blocks, at small block separations and small deviations from bulk gas-liquid coexistence, we observe a strongly attractive (near constant) force, stemming from capillary evaporation to form a low density gas-like intrusion between the blocks. The accompanying $\chi({\mathbf r})$ exhibits structure which reflects the incipient gas-liquid interfaces that develop. We argue that our model system provides a means to understanding the basic physics of solvent mediated interactions between nanostructures, and between objects such as proteins in water, that possess hydrophobic and hydrophilic patches.Comment: 19 pages, 21 figure

Relationship between Local Molecular Field Theory and Density Functional Theory for non-uniform liquids

The Local Molecular Field Theory (LMF) developed by Weeks and co-workers has proved successful for treating the structure and thermodynamics of a variety of non-uniform liquids. By reformulating LMF in terms of one-body direct correlation functions we recast the theory in the framework of classical Density Functional Theory (DFT). We show that the general LMF equation for the effective reference potential phi_R follows directly from the standard mean-field DFT treatment of attractive interatomic forces. Using an accurate (Fundamental Measures) DFT for the non-uniform hard-sphere reference fluid we determine phi_R for a hard-core Yukawa liquid adsorbed at a planar hard wall. In the approach to bulk liquid-gas coexistence we find the effective potentials exhibit rich structure that can include damped oscillations at large distances from the wall as well as the repulsive hump near the wall required to generate the low density 'gas' layer characteristic of complete drying. We argue that it would be difficult to obtain the same level of detail from other (non DFT based) implementations of LMF. LMF emphasizes the importance of making an intelligent division of the interatomic pair potential of the full system into a reference part and a remainder that can be treated in mean-field approximation. We investigate different divisions for an exactly solvable one- dimensional model where the pair potential has a hard-core plus a linear attractive tail. Results for the structure factor and the equation of state of the uniform fluid show that including a significant portion of the attraction in the reference system can be much more accurate than treating the full attractive tail in mean-field approximation. We discuss further aspects of the relationship between LMF and DFT.Comment: 35 pages, 10 Fig

Mean-field dynamical density functional theory

We examine the out-of-equilibrium dynamical evolution of density profiles of ultrasoft particles under time-varying external confining potentials in three spatial dimensions. The theoretical formalism employed is the dynamical density functional theory (DDFT) of Marini Bettolo Marconi and Tarazona [J. Chem. Phys. {\bf 110}, 8032 (1999)], supplied by an equilibrium excess free energy functional that is essentially exact. We complement our theoretical analysis by carrying out extensive Brownian Dynamics simulations. We find excellent agreement between theory and simulations for the whole time evolution of density profiles, demonstrating thereby the validity of the DDFT when an accurate equilibrium free energy functional is employed.Comment: 8 pagers, 4 figure

Phase behavior of a fluid with competing attractive and repulsive interactions

Fluids in which the interparticle potential has a hard core, is attractive at moderate separations, and repulsive at greater separations are known to exhibit novel phase behavior, including stable inhomogeneous phases. Here we report a joint simulation and theoretical study of such a fluid, focusing on the relationship between the liquid-vapor transition line and any new phases. The phase diagram is studied as a function of the amplitude of the attraction for a certain fixed amplitude of the long ranged repulsion. We find that the effect of the repulsion is to substitute the liquid-vapor critical point and a portion of the associated liquid-vapor transition line, by two first order transitions. One of these transitions separates the vapor from a fluid of spherical liquidlike clusters; the other separates the liquid from a fluid of spherical voids. At low temperature, the two transition lines intersect one another and a vapor-liquid transition line at a triple point. While most integral equation theories are unable to describe the new phase transitions, the Percus Yevick approximation does succeed in capturing the vapor-cluster transition, as well as aspects of the structure of the cluster fluid, in reasonable agreement with the simulation results.Comment: 15 pages, 20 figure

The standard mean-field treatment of inter-particle attraction in classical DFT is better than one might expect

In classical density functional theory (DFT) the part of the Helmholtz free energy functional arising from attractive inter-particle interactions is often treated in a mean-field or van der Waals approximation. On the face of it, this is a somewhat crude treatment as the resulting functional generates the simple random phase approximation (RPA) for the bulk fluid pair direct correlation function. We explain why using standard mean-field DFT to describe inhomogeneous fluid structure and thermodynamics is more accurate than one might expect based on this observation. By considering the pair correlation function $g(x)$ and structure factor $S(k)$ of a one-dimensional model fluid, for which exact results are available, we show that the mean-field DFT, employed within the test-particle procedure, yields results much superior to those from the RPA closure of the bulk Ornstein-Zernike equation. We argue that one should not judge the quality of a DFT based solely on the approximation it generates for the bulk pair direct correlation function.Comment: 9 pages, 3 figure

Structure, phase behavior and inhomogeneous fluid properties of binary dendrimer mixtures

The effective pair potentials between different kinds of dendrimers in solution can be well approximated by appropriate Gaussian functions. We find that in binary dendrimer mixtures the range and strength of the effective interactions depend strongly upon the specific dendrimer architecture. We consider two different types of dendrimer mixtures, employing the Gaussian effective pair potentials, to determine the bulk fluid structure and phase behavior. Using a simple mean field density functional theory (DFT) we find good agreement between theory and simulation results for the bulk fluid structure. Depending on the mixture, we find bulk fluid-fluid phase separation (macro-phase separation) or micro-phase separation, i.e., a transition to a state characterized by undamped periodic concentration fluctuations. We also determine the inhomogeneous fluid structure for confinement in spherical cavities. Again, we find good agreement between the DFT and simulation results. For the dendrimer mixture exhibiting micro-phase separation, we observe rather striking pattern formation under confinement.Comment: 8 pages, 10 figure

Dynamical density functional theory for dense atomic liquids

Starting from Newton's equations of motion, we derive a dynamical density functional theory (DDFT) applicable to atomic liquids. The theory has the feature that it requires as input the Helmholtz free energy functional from equilibrium density functional theory. This means that, given a reliable equilibrium free energy functional, the correct equilibrium fluid density profile is guaranteed. We show that when the isothermal compressibility is small, the DDFT generates the correct value for the speed of sound in a dense liquid. We also interpret the theory as a dynamical equation for a coarse grained fluid density and show that the theory can be used (making further approximations) to derive the standard mode coupling theory that is used to describe the glass transition. The present theory should provide a useful starting point for describing the dynamics of inhomogeneous atomic fluids.Comment: 14 pages, accepted for publication in J. Phys.: Condens. Matte