Browsing by Subject "liquid"

Now showing 1 - 7 of 7

Anomalous structure and dynamics of the Gaussian-core fluid
(2009-04) Krekelberg, William P.; Kumar, Tanuj; Mittal, Jeetain; Errington, Jeffrey R.; Truskett, Thomas M.; Krekelberg, William P.; Kumar, Tanuj; Truskett, Thomas M.
It is known that there are thermodynamic states for which the Gaussian-core fluid displays anomalous properties such as expansion upon isobaric cooling (density anomaly) and increased single-particle mobility upon isothermal compression (self-diffusivity anomaly). Here, we investigate how temperature and density affect its short-range translational structural order, as characterized by the two-body excess entropy. We find that there is a wide range of conditions for which the short-range translational order of the Gaussian-core fluid decreases upon isothermal compression (structural order anomaly). As we show, the origin of the structural anomaly is qualitatively similar to that of other anomalous fluids (e.g., water or colloids with short-range attractions) and is connected to how compression affects static correlations at different length scales. Interestingly, we find that the self-diffusivity of the Gaussian-core fluid obeys a scaling relationship with the two-body excess entropy that is very similar to the one observed for a variety of simple liquids. One consequence of this relationship is that the state points for which structural, self-diffusivity, and density anomalies of the Gaussian-core fluid occur appear as cascading regions on the temperature-density plane; a phenomenon observed earlier for models of waterlike fluids. There are, however, key differences between the anomalies of Gaussian-core and waterlike fluids, and we discuss how those can be qualitatively understood by considering the respective interparticle potentials of these models. Finally, we note that the self-diffusivity of the Gaussian-core fluid obeys different scaling laws depending on whether the two-body or total excess entropy is considered. This finding, which deserves more comprehensive future study, appears to underscore the significance of higher-body correlations for the behavior of fluids with bounded interactions.
Broadband boundary effects on Brownian motion
(2015-12) Mo, Jianyong; Simha, Akarsh; Raizen, Mark G.; Mo, Jianyong; Simha, Akarsh; Raizen, Mark G.
Brownian motion of particles in confined fluids is important for many applications, yet the effects of the boundary over a wide range of time scales are still not well understood. We report high-bandwidth, comprehensive measurements of Brownian motion of an optically trapped micrometer-sized silica sphere in water near an approximately flat wall. At short distances we observe anisotropic Brownian motion with respect to the wall. We find that surface confinement not only occurs in the long time scale diffusive regime but also in the short time scale ballistic regime, and the velocity autocorrelation function of the Brownian particle decays faster than that of a particle in bulk fluid. Furthermore, at low frequencies the thermal force loses its color due to the reflected flow from the no-slip boundary. The power spectrum of the thermal force on the particle near a no-slip boundary becomes flat at low frequencies. This detailed understanding of boundary effects on Brownian motion opens a door to developing a 3D microscope using particles as remote sensors.
Flow coupling during three-phase gravity drainage
(2011-06) Dehghanpour, H.; Aminzadeh, B.; Mirzaei, M.; DiCarlo, D. A.; Dehghanpour, H.; Aminzadeh, B.; Mirzaei, M.; DiCarlo, D. A.
We measure the three-phase oil relative permeability k(ro) by conducting unsteady-state drainage experiments in a 0.8 m water-wet sand pack. We find that when starting from capillary-trapped oil, k(ro) shows a strong dependence on both the flow of water and the water saturation and a weak dependence on oil saturation, contrary to most models. The observed flow coupling between water and oil is stronger in three-phase flow than two-phase flow, and cannot be observed in steady-state measurements. The results suggest that the oil is transported through moving gas-oil-water interfaces (form drag) or momentum transport across stationary interfaces (friction drag). We present a simple model of friction drag which compares favorably to the experimental data.
Generalized Rosenfeld scalings for tracer diffusivities in not-so-simple fluids: Mixtures and soft particles
(2009-12) Krekelberg, William P.; Pond, Mark J.; Goel, Gaurav; Shen, Vincent K.; Errington, Jeffrey R.; Truskett, Thomas M.; Krekelberg, William P.; Pond, Mark J.; Goel, Gaurav; Truskett, Thomas M.
Rosenfeld [Phys. Rev. A 15, 2545 (1977)] originally noticed that casting the transport coefficients of simple monatomic equilibrium fluids in a specific dimensionless form makes them approximately single-valued functions of excess entropy. This observation has predictive value because, while the transport coefficients of dense fluids can be difficult to estimate from first principles, the excess entropy can often be accurately predicted from liquid-state theory. In this work, we use molecular simulations to investigate whether Rosenfeld's observation is a special case of a more general scaling law relating the tracer diffusivities of particles in mixtures to the excess entropy. Specifically, we study the tracer diffusivities, static structure, and thermodynamic properties of a variety of one- and two-component model fluid systems with either additive or nonadditive interactions of the hard-sphere or Gaussian-core form. The results of the simulations demonstrate that the effects of mixture concentration and composition, particle-size asymmetry and additivity, and strength of the interparticle interactions in these fluids are consistent with an empirical scaling law relating the excess entropy to a dimensionless (generalized Rosenfeld) form of tracer diffusivity, which we introduce here. The dimensionless form of the tracer diffusivity follows from knowledge of the intermolecular potential and the transport/thermodynamic behavior of fluids in the dilute limit. The generalized Rosenfeld scaling requires less information and provides more accurate predictions than either Enskog theory or scalings based on the pair-correlation contribution to the excess entropy. As we show, however, it also suffers from some limitations especially for systems that exhibit significant decoupling of individual component tracer diffusivities.
Harmonic moment dynamics in Laplacian growth
(2010-01) Leshchiner, Alexander; Thrasher, Matthew; Mineev-Weinstein, Mark B.; Swinney, Harry L.; Leshchiner, Alexander; Thrasher, Matthew; Swinney, Harry L.
Harmonic moments are integrals of integer powers of z=x+iy over a domain. Here, the domain is an exterior of a bubble of air growing in an oil layer between two horizontal closely spaced plates. Harmonic moments are a natural basis for such Laplacian growth phenomena because, unlike other representations, these moments linearize the zero surface tension problem [S. Richardson, J. Fluid Mech. 56, 609 (1972)], so that all moments except the lowest one (the area of the bubble) are conserved in time. In our experiments, we directly determine the harmonic moments and show that for nonzero surface tension, all moments (except the lowest one) decay in time rather than exhibiting the divergences of other representations. Further, we derive an expression that relates the derivative of the k(th) harmonic moment M(k) to measurable quantities (surface tension, viscosity, the distance between the plates, and a line integral over the contour encompassing the growing bubble). The laboratory observations are in good accord with the expression we derive for dM(k)/dt, which is proportional to the surface tension; thus in the zero surface tension limit, the moments (above k=0) are all conserved, in accord with Richardson's theory. In addition, from the measurements of the time evolution of the harmonic moments we obtain a value for the surface tension that is within 20% of the accepted value. In conclusion, our analysis and laboratory observations demonstrate that an interface dynamics description in terms of harmonic moments is physically realizable and robust.
Modeling Subsurface Biodegradation of Non-Aqueous Phase Liquids: A Literature Review
(University of Texas at Austin, 1995-02) de Blanc, P.C.; McKinney, D.C.; Speitel, G.E. Jr
Structural anomalies of fluids: Origins in second and higher coordination shells
(2008-04) Krekelberg, William P.; Mittal, Jeetain; Ganesan, Venkat; Truskett, Thomas M.; Krekelberg, William P.|Ganesan, Venkat; Truskett, Thomas M.
Compressing or cooling a fluid typically enhances its static interparticle correlations. However, there are notable exceptions. Isothermal compression can reduce the translational order of fluids that exhibit anomalous waterlike trends in their thermodynamic and transport properties, while isochoric cooling (or strengthening of attractive interactions) can have a similar effect on fluids of particles with short-range attractions. Recent simulation studies by Yan [Phys. Rev. E 76, 051201 (2007)] on the former type of system and Krekelberg [J. Chem. Phys. 127, 044502 (2007)] on the latter provide examples where such structural anomalies can be related to specific changes in second and more distant coordination shells of the radial distribution function. Here, we confirm the generality of this microscopic picture through analysis, via molecular simulation and integral equation theory, of coordination shell contributions to the two-body excess entropy for several related model fluids which incorporate different levels of molecular resolution. The results suggest that integral equation theory can be an effective and computationally inexpensive tool for assessing, based on the pair potential alone, whether new model systems are good candidates for exhibiting structural (and hence thermodynamic and transport) anomalies.