Subir K. Das

Curvature dependence of surface free energy of liquid drops and bubbles: A simulation study

We study the excess free energy due to phase coexistence of fluids by Monte Carlo simulations using successive umbrella sampling in finite L×L×L boxes with periodic boundary conditions. Both the vapor-liquid phase coexistence of a simple Lennard-Jones fluid and the coexistence between A-rich and B-rich phases of a symmetric binary (AB) Lennard-Jones mixture are studied, varying the density ρ in the simple fluid or the relative concentration x(A) of A in the binary mixture, respectively. The character of phase coexistence changes from a spherical droplet (or bubble) of the minority phase (near the coexistence curve) to a cylindrical droplet (or bubble) and finally (in the center of the miscibility gap) to a slablike configuration of two parallel flat interfaces. Extending the analysis of Schrader et al., [Phys. Rev. E 79, 061104 (2009)], we extract the surface free energy γ(R) of both spherical and cylindrical droplets and bubbles in the vapor-liquid case and present evidence that for R→∞ the leading order (Tolman) correction for droplets has sign opposite to the case of bubbles, consistent with the Tolman length being independent on the sign of curvature. For the symmetric binary mixture, the expected nonexistence of the Tolman length is confirmed. In all cases and for a range of radii R relevant for nucleation theory, γ(R) deviates strongly from γ(∞) which can be accounted for by a term of order γ(∞)/γ(R)-1∝R(-2). Our results for the simple Lennard-Jones fluid are also compared to results from density functional theory, and we find qualitative agreement in the behavior of γ(R) as well as in the sign and magnitude of the Tolman length.

Influence of chemical short-range order on atomic diffusion in Al–Ni melts

We use inelastic neutron scattering and molecular dynamics simulation to investigate the chemical short-range order (CSRO), visible through prepeaks in the structure factors, and its relation to self-diffusion in Al–Ni melts. As a function of composition at 1795K, Ni self-diffusion coefficients from experiment and simulation exhibit a nonlinear dependence with a pronounced increase on the Al-rich side. This comes along with a change in CSRO with increasing Al content that is related to a more dense packing of the atoms in Ni-rich Al–Ni systems.

Self-diffusion and interdiffusion in Al80Ni20 melts : Simulation and experiment

A combination of experimental techniques and molecular dynamics (MD) computer simulation is used to investigate the diffusion dynamics in Al 80 Ni 20 melts. Experimentally, the self-diffusion coefficient of Ni is measured by the long-capillary (LC) method and by quasielastic neutron scattering. The LC method yields also the interdiffusion coefficient. Whereas the experiments were done in the normal liquid state, the simulations provided the determination of both self-diffusion and interdiffusion constants in the undercooled regime as well. The simulation results show good agreement with the experimental data. In the temperature range 3000 K ≥ T ≥ 715 K, the interdiffusion coefficient is larger than the self-diffusion constants. Furthermore the simulation shows that this difference becomes larger in the undercooled regime. This result can be refered to a relatively strong temperature dependence of the thermodynamic factor Φ, which describes the thermodynamic driving force for interdiffusion. The simulations also indicate that the Darken equation is a good approximation, even in the undercooled regime. This implies that dynamic cross correlations play a minor role for the temperature range under consideration.

Static and dynamic critical behavior of a symmetrical binary fluid: a computer simulation.

A symmetrical binary, A+B Lennard-Jones mixture is studied by a combination of semi-grand-canonical Monte Carlo (SGMC) and molecular dynamics (MD) methods near a liquid-liquid critical temperature T(c). Choosing equal chemical potentials for the two species, the SGMC switches identities (A-->B-->A) to generate well-equilibrated configurations of the system on the coexistence curve for TT(c). A finite-size scaling analysis of the concentration susceptibility above T(c) and of the order parameter below T(c) is performed, varying the number of particles from N=400 to 12 800. The data are fully compatible with the expected critical exponents of the three-dimensional Ising universality class. The equilibrium configurations from the SGMC runs are used as initial states for microcanonical MD runs, from which transport coefficients are extracted. Self-diffusion coefficients are obtained from the Einstein relation, while the interdiffusion coefficient and the shear viscosity are estimated from Green-Kubo expressions. As expected, the self-diffusion constant does not display a detectable critical anomaly. With appropriate finite-size scaling analysis, we show that the simulation data for the shear viscosity and the mutual diffusion constant are quite consistent both with the theoretically predicted behavior, including the critical exponents and amplitudes, and with the most accurate experimental evidence.

Critical Dynamics in a Binary Fluid: Simulations and Finite-size Scaling

We report comprehensive simulations of the critical dynamics of a symmetric binary Lennard-Jones mixture near its consolute point. The self-diffusion coefficient exhibits no detectable anomaly. The data for the shear viscosity and the mutual-diffusion coefficient are fully consistent with the asymptotic power laws and amplitudes predicted by renormalization-group and mode-coupling theories provided finite-size effects and the background contribution to the relevant Onsager coefficient are suitably accounted for. This resolves a controversy raised by recent molecular simulations.

Transport phenomena and microscopic structure in partially miscible binary fluids: A simulation study of the symmetrical Lennard-Jones mixture

Static and dynamic structure factors and various transport coefficients are computed for a Lennard-Jones model of a binary fluid (A,B) with a symmetrical miscibility gap, varying both the temperature and relative concentration of the mixture. The model is first equilibrated by a semi-grandcanonical Monte Carlo method, choosing the temperature and chemical potential difference Δμ between the two species as the given independent variables. Varying for Δμ=0 the temperature and particle number N over a wide range, the location of the coexistence curve in the thermodynamic limit is estimated. Well-equilibrated configurations from these Monte Carlo runs are used as initial states for microcanonical molecular dynamics runs, in order to study the microscopic structure and the behavior of transport coefficients as well as dynamic correlation functions along the coexistence curve. Dynamic structure factors Sαβ(q,t) [and the corresponding static functions Sαβ(q)] are recorded (α,β∈A,B), q being the wave number and t...

Does Young's equation hold on the nanoscale? A Monte Carlo test for the binary Lennard-Jones fluid

When a phase-separated binary (A+B) mixture is exposed to a wall, that preferentially attracts one of the components, interfaces between A-rich and B-rich domains in general meet the wall making a contact angle ?. Youngs equation describes this angle in terms of a balance between the A-B interfacial tension ?AB and the surface tensions ?wA, ?wB between, respectively, the A- and B-rich phases and the wall, ?ABcos??=?wA??wB. By Monte Carlo simulations of bridges, formed by one of the components in a binary Lennard-Jones liquid, connecting the two walls of a nanoscopic slit pore, ? is estimated from the inclination of the interfaces, as a function of the wall-fluid interaction strength. The information on the surface tension difference ?wA??wB are obtained independently from a new thermodynamic integration method, while ?AB is found from the finite-size scaling analysis of the concentration distribution function. We show that Youngs equation describes the contact angles of the actual nanoscale interfaces for this model rather accurately and the location of the (first-order) wetting transition is estimated.

Phase behavior of active swimmers in depletants: molecular dynamics and integral equation theory.

We study the structure and phase behavior of a binary mixture where one of the components is self-propelling in nature. The interparticle interactions in the system are taken from the Asakura-Oosawa model for colloid-polymer mixtures for which the phase diagram is known. In the current model version, the colloid particles are made active using the Vicsek model for self-propelling particles. The resultant active system is studied by molecular dynamics methods and integral equation theory. Both methods produce results consistent with each other and demonstrate that the Vicsek model-based activity facilitates phase separation, thus, broadening the coexistence region.

Universality in fluid domain coarsening: The case of vapor-liquid transition

Domain growth during the kinetics of phase separation is studied following vapor-liquid transition in a single component Lennard-Jones fluid. Results are analyzed after appropriately mapping the continuum snapshots obtained from extensive molecular-dynamics simulations to a simple cubic lattice. For near-critical quench interconnected domain morphology is observed. A brief period of slow diffusive growth is followed by a linear viscous hydrodynamic growth that lasts for an extended period of time. This result is in contradiction with earlier reports of late-time growth exponent 1/2 that questions the uniqueness of the non-equilibrium universality for liquid-liquid and vapor-liquid transitions.

Spinodal decomposition in thin films: molecular-dynamics simulations of a binary Lennard-Jones fluid mixture

We use molecular dynamics (MD) to simulate an unstable homogeneous mixture of binary fluids (AB), confined in a slit pore of width D. The pore walls are assumed to be flat and structureless and attract one component of the mixture (A) with the same strength. The pairwise interactions between the particles are modeled by the Lennard-Jones potential, with symmetric parameters that lead to a miscibility gap in the bulk. In the thin-film geometry, an interesting interplay occurs between surface enrichment and phase separation. We study the evolution of a mixture with equal amounts of A and B, which is rendered unstable by a temperature quench. We find that A-rich surface enrichment layers form quickly during the early stages of the evolution, causing a depletion of A in the inner regions of the film. These surface-directed concentration profiles propagate from the walls towards the center of the film, resulting in a transient layered structure. This layered state breaks up into a columnar state, which is characterized by the lateral coarsening of cylindrical domains. The qualitative features of this process resemble results from previous studies of diffusive Ginzburg-Landau-type models [S. K. Das, S. Puri, J. Horbach, and K. Binder, Phys. Rev. E 72, 061603 (2005)], but quantitative aspects differ markedly. The relation to spinodal decomposition in a strictly two-dimensional geometry is also discussed.