Coarse-grained polarizable soft solvent models, with applications in dissipative particle dynamics.

We critically examine a broad class of explicitly polarizable soft solvent models aimed at applications in dissipative particle dynamics. We obtain the dielectric permittivity using the fluctuating box dipole method in linear response theory and verify the models in relation to several test cases, including demonstrating ion desorption from an oil-water interface due to image charge effects. We additionally compute the Kirkwood factor and find that it uniformly lies in the range gK≃0.7-0.8, indicating that dipole-dipole correlations are not negligible in these models. This is supported by the measurements of dipole-dipole correlation functions. As a consequence, Onsager theory over-predicts the dielectric permittivity by 20%-30%. The mean square molecular dipole moment can be accurately estimated with a first-order Wertheim perturbation theory.

Local density dependent potentials for an underlying van der Waals equation of state: A simulation and density functional theory analysis.

There is an ever increasing use of local density dependent potentials in the mesoscale modeling of complex fluids. Questions remain, though, about the dependence of the thermodynamic and structural properties of such systems on the cutoff distance used to calculate these local densities. These questions are particularly acute when it comes to the stability and structure of the vapor/liquid interface. In this article, we consider local density dependent potentials derived from an underlying van der Waals equation of state. We use simulation and density functional theory to examine how the bulk thermodynamic and interfacial properties vary with the cutoff distance, rc, used to calculate the local densities. We show quantitatively how the simulation results for bulk thermodynamic properties and vapor-liquid equilibrium approach the van der Waals limit as rc increases and demonstrate a scaling law for the radial distribution function in the large rc limit. We show that the vapor-liquid interface is stable with a well-defined surface tension and that the interfacial density profile is oscillatory, except for temperatures close to critical. Finally, we show that in the large rc limit, the interfacial tension is proportional to rc and, therefore, unlike the bulk thermodynamic properties, does not approach a constant value as rc increases. We believe that these results give new insights into the properties of local density dependent potentials, in particular their unusual interfacial behavior, which is relevant for modeling complex fluids in soft matter.

Microstructural and thermodynamic characterization of wormlike micelles formed by polydisperse ionic surfactant solutions.

For industrial applications of self-assembled wormlike micelles, measurement and characterization of a micellar material's microstructure and rheology are paramount for the development and deployment of new high-performing and cost-effective formulations. Within this workflow, there are significant bottlenecks associated with experimental delays and a lack of transferability of results from one chemistry to another. In this work, we outline a process to predict microscopic and thermodynamic characteristics of wormlike micelles directly from rheological data by combining a more robust and efficient fitting algorithm with a recently published constitutive model called the Toy Shuffling model [J. D. Peterson and M. E. Cates, J. Rheol. 64, 1465-1496 (2020) and J. D. Peterson and M. E. Cates, J. Rheol. 65, 633-662 (2021)]. To support this work, linear rheology measurements were taken for 143 samples comprising a common base formulation of commercial sodium lauryl ether sulfate, cocamidopropyl betaine, and salt (NaCl). The steady state zero shear viscosity evident in linear rheology was measured in duplicate via direct steady and oscillatory shear experiments. Fitting the collected data to the model, we found trends in the microstructural and thermodynamic characteristics that agree with molecular dynamics simulations. These trends validate our new perspective on the parameters that inform the study of the relationship between chemical formulation and rheology. This work, when implemented at scale, can potentially be used to inform and test strategies for predicting self-assembled micellar structures based on chemical formulation.

Phase behaviour of hard board-like particles.

We examine the phase behaviour of colloidal suspensions of hard board-like particles (HBPs) as a function of their shape anisotropy, and observe a fascinating spectrum of nematic, smectic, and columnar liquid-crystalline phases, whose formation is entirely driven by excluded volume effects. We map out the phase diagram of short and long HBPs by gradually modifying their shape from prolate to oblate and investigate the long-range order of the resulting morphologies along the phase directors and perpendicularly to them. The intrinsic biaxial nature of these particles promotes the formation of translationally ordered biaxial phases, but does not show solid evidence that it would, per se, promote the formation of the biaxial nematic phase. Our simulations shed light on the controversial existence of the discotic smectic phase, whose layers are as thick as the minor particle dimension, which is stable in a relatively large portion of our phase diagrams. Additionally, we modify the Onsager theory to describe the isotropic-nematic phase transition of freely rotating biaxial particles as a function of the particle width, and find a relatively strong first-order signature, in excellent agreement with our simulations. In an attempt to shed light on the elusive formation of the biaxial nematic phase, we apply this theory to predict the uniaxial-biaxial nematic phase transition and confirm, again in agreement with simulations, the prevailing stability of the translationally ordered smectic phase over the orientationally ordered biaxial nematic phase.

Macroscopic chiral symmetry breaking in monolayers of achiral nonconvex platelets.

The fabrication of chiral structures using achiral building blocks is a fundamental problem that remains a challenge in materials science. In this work we present a molecular dynamics simulation study of nonconvex polygonal platelets, interacting via soft-repulsive interactions, that are confined in two-dimensional space. These particle models are designed to promote, even at moderate densities, a natural offset displacement between the edges of neighbouring particles. In particular we demonstrate that nonconvex platelets exhibit macroscopic chiral symmetry breaking when the symmetry of the particles equals (or is multiple of) the number of nearest neighbours in the condensed crystalline phase, corresponding to the situation of platelets with 4-, 6-, and 12-fold symmetries.

Thermodynamics of the self-assembly of non-ionic chromonic molecules using atomistic simulations. The case of TP6EO2M in aqueous solution.

Atomistic molecular dynamic simulations have been performed for the non-ionic chromonic liquid crystal 2,3,6,7,10,11-hexa-(1,4,7-trioxa-octyl)-triphenylene (TP6EO2M) in aqueous solution. TP6EO2M molecules consist of a central poly-aromatic core (a triphenylene ring) functionalized by six hydrophilic ethyleneoxy (EO) chains, and have a strong tendency to aggregate face-to-face into stacks even in very dilute solution. We have studied self-assembly of the molecules in the low concentration range corresponding to an isotropic solution of aggregates, using two force fields GAFF and OPLS. Our results reveal that the GAFF force field, even though it was successfully used previously for modelling of ionic chromonics, overestimates the attraction of TP6EO2M molecules in water. This results in an aggregation free energy which is too high, a reduced hydration of EO chains and, therefore, molecular self-assembly into compact disordered clusters instead of stacks. In contrast, use of the OPLS force field, leads to self-assembly into ordered stacks in agreement with earlier experimental studies of triphenylene-based chromonics. The free energy of association follows a "quasi-isodesmic" pattern, where the binding free energy of two molecules to form a dimer is of the order of 2.5 RT larger than the corresponding energy of addition of a molecule into a stack. The obtained value for the binding free energy, ΔG=-12 RT, is found to be in line with the published values for typical ionic chromonics (-7 to -12 RT), and agrees reasonably well with the experimental results for this system. The calculated interlayer distance between the molecules in a stack is 0.37 nm, which is at the top of the range found for typical chromonics (0.33-0.37 nm). We suggest that the relatively large layer spacing can be attributed to the repulsion between EO side chains.

Self-assembly and mesophase formation in a non-ionic chromonic liquid crystal system: insights from dissipative particle dynamics simulations.

Results are presented from a dissipative particle dynamics (DPD) simulation of a model non-ionic chromonic system, TP6EO2M, composed of a poly(ethylene glycol) functionalised aromatic (triphenylene) core. The simulations demonstrate self-assembly of chromonic molecules to form single molecule stacks in solution at low concentrations, the formation of a nematic mesophase at higher concentrations and a columnar phase in the more concentrated regime. The simulation model used allows very large system sizes, of many thousands of particles, to be studied. This provides, for the first time, an opportunity to study chromonic phase behaviour by simulation without severe restrictions imposed by system size. In the low concentration limit, the simulations demonstrate approximate isodesmic association from which a binding energy can be obtained, allowing the simulations to be tuned to reproduce the behaviour of the real experimental system.

Platelet counting with the BD Accuri(TM) C6 flow cytometer.

The Accuri™ C6 is a compact flow cytometer that uses a peristaltic pump with a laminar flow fluidic system and can measure absolute cell counts. In this study we have evaluated this method with the International Reference Method (IRM) simultaneously measured on both the Accuri™ C6 and a reference flow cytometer. After optimisation of sample labelling conditions, final dilutions and flow cytometer settings, a comparison of the absolute fluorescent platelet count with the RBC/platelet ratio on the C6 and the IRM was then performed in 144 patient samples with a full range of platelet counts (range 2-650 × 10(9)/l). The platelet/RBC ratio method determined on the Accuri™ agreed well with the IRM (R(2)=0.99, bias=2.3 (Bland Altman) and R(2)=0.96, bias=1.02 at counts <50 × 10(9)/l). The absolute platelet count also agreed well with the IRM (R(2)=0.97, bias=-0.16 and R(2)=0.91, bias=3.7 at <50 × 10(9)/l). The C6 absolute platelet count and RBC/platelet ratio methods also agreed well (R(2)=0.99, bias=-2.5 and R(2)=0.95, bias=2.71 at counts <50 × 10(9)/l). Reproducibility studies on the C6 gave CVs of <5% for the RB/platelet ratio and <12% for the absolute cell counts. The C6 also demonstrated excellent linearity on diluted samples with both volume and ratio methods (R(2)=0.99). As one might expect, the absolute platelet count is therefore slightly more inaccurate than the RBC/platelet ratio particularly at platelet counts <50 × 10(9)/l as it is likely to be more sensitive to pipetting error. The Accuri™ C6 provides a simple, rapid and reliable method for measuring platelet counts by either the RBC/platelet or direct volume methods. The direct volume method can also be used to determine platelet counts within purified platelet preparations or concentrates in the absence of RBC.

The Management of Dysfunctional Gallbladder Disease and the Role of Laparoscopic Cholecystectomy on Symptom Improvement: A Retrospective Cohort Study.

Background Biliary dyskinesia (BD) is a disorder characterised by abdominal pain of biliary origin (i.e., sudden steady pain at the right upper quadrant of the abdomen or the epigastrium, the absence of gallstones on ultrasound (US)), and a decreased gallbladder ejection fraction (GBEF) on a cholecystokinin-cholescintigraphy hepatobiliary iminodiacetic acid (CCK-HIDA) scan. Patients experiencing symptoms suggestive of biliary obstruction, but lacking gallstones, yet exhibiting abnormal gallbladder emptying, may find therapeutic benefit from laparoscopic cholecystectomy. Common symptoms include recurrent, intense, and enduring pain, often exacerbated by fatty food consumption, localised in the upper right quadrant or epigastric region. This pain may radiate to the back or shoulder, persisting for at least 30 minutes but not exceeding several hours, and it is sometimes accompanied by nausea and vomiting. Abnormal gallbladder emptying is typically indicated by a GBEF below 35% on cholescintigraphy following cholecystokinin administration. Objective This study represents a single-centric review focusing on 88 patients over a five-year period who presented with features of dysfunctional gallbladder and underwent cholescintigraphy. The primary aim was to identify whether there is any role for laparoscopic cholecystectomy in symptom improvement among these patients. Methods This was a retrospective cohort study involving data collection using electronic medical records. Eighty-eight patients who underwent the HIDA scan between January 2019 and December 2023 at Wirral University Teaching Hospital NHS Foundation Trust (WUTH) were identified and separated into two groups, either hypofunctioning gallbladder (EF<35% ) or hyperfunctioning gallbladder (EF>80%). Normal HIDA scan patients (EF between 35%-80%) were excluded. The frequency of laparoscopic cholecystectomy and subsequent symptom improvement were recorded. Results Fifty-one patients were diagnosed with gallbladder dyskinesia (BD). Of these, 36 patients (30 females, mean age 43) were diagnosed with hypofunctional gallbladder (EF<35%), where 17 patients underwent laparoscopic cholecystectomy, resulting in symptom improvement in 10 patients (58.8%). Conversely, 15 patients were diagnosed with hyperfunctional gallbladder (13 females, mean age 48.6). Only two patients (13%) underwent laparoscopic cholecystectomy with 100% symptom improvement in both patients. Conclusions In conclusion, our retrospective study highlights the significance of the HIDA scan in identifying gallbladder hypofunction among patients presenting with biliary symptoms. The findings establish the efficacy of laparoscopic cholecystectomy as a management approach, with a notable proportion of patients experiencing symptom improvement (58.8%). These results contribute to our understanding of biliary dysfunction management and emphasise the importance of individualised treatment strategies for optimal patient outcomes. Further, randomised controlled trials (RCTs) are warranted to validate these findings and explore additional factors influencing symptom resolution in this patient population.

Phase behaviour and the random phase approximation for ultrasoft restricted primitive models.

Phase separation of the ultrasoft restricted primitive model (URPM) with gaussian charges is re-investigated in the random phase approximation (RPA)--the "Level A" approximation discussed by Nikoubashman, Hansen, and Kahl [J. Chem. Phys. 137, 094905 (2012)]. We find that the RPA predicts a region of low temperature vapour-liquid coexistence, with a critical density much lower than that observed in either simulations or more refined approximations (we also remark that the RPA critical point for a related model with Bessel charges can be solved analytically). This observation suggests that the hierarchy of approximations introduced by Nikoubashman et al. should be analogous to those introduced by Fisher and Levin for the restricted primitive model [Phys. Rev. Lett. 71, 3826 (1993)], which makes the inability of these approximations to capture the observed URPM phase behaviour even more worthy of investigation.

Screening properties of Gaussian electrolyte models, with application to dissipative particle dynamics.

We investigate the screening properties of Gaussian charge models of electrolyte solutions by analysing the asymptotic behaviour of the pair correlation functions. We use a combination of Monte Carlo simulations with the hyper-netted chain integral equation closure, and the random phase approximation, to establish the conditions under which a screening length is well defined and the extent to which it matches the expected Debye length. For practical applications, for example, in dissipative particle dynamics, we are able to summarise our results in succinct rules-of-thumb which can be used for mesoscale modeling of electrolyte solutions. We thereby establish a solid foundation for future work, such as the systematic incorporation of specific ion effects.

Hierarchical Aggregation in a Complex Fluid─The Role of Isomeric Interconversion.

There is an ever-increasing body of evidence that metallic complexes involving amphiliphic ligands do not form normal solutions in organic solvents. Instead, they form complex fluids with intricate structures. For example, the metallic complexes may aggregate into clusters, and these clusters themselves may aggregate into superclusters. To gain a deeper insight into the mechanisms at play, we have used an improved force field to conduct extensive molecular dynamics simulations of a system composed of zirconium nitrate, water, nitric acid, tri-n-butyl phosphate, and n-octane. The important new finding is that a dynamic equilibrium between the cis and trans isomers of the metal complex is likely to play a key role in the aggregation behavior. The isolated cis and trans isomers have similar energies, but simulation indicates that the clusters consist predominantly of cis isomers. With increasing metal concentration, we hypothesize that more clustering occurs and the chemical equilibrium shifts toward the cis isomer. It is possible that such isomeric effects play a role in the liquid-liquid extraction of other species and the inclusion of such effects in flow sheet modeling may lead to a better description of the process.

Molecular Dynamics Study of the Aggregation Behavior of N,N,N',N'-Tetraoctyl Diglycolamide.

Liquid-liquid extraction is a commonly used technique to separate metals and is a process that has particular relevance to the nuclear industry. There has been a drive to use environmentally friendly ligands composed only of carbon, hydrogen, nitrogen, and oxygen. One example is the i-SANEX process that has been developed to separate minor actinides from spent nuclear fuel. The underlying science of such processes, is, however, both complex and intriguing. Recent research indicates that the liquid phases involved are frequently structured fluids with a hierarchical organization of aggregates. Effective flow-sheet modeling of such processes is likely to benefit from the knowledge of the fundamental properties of these phases. As a stepping stone toward this, we have performed molecular dynamics simulations on a metal free i-SANEX system composed of the ligand N,N,N',N'-tetraoctyl diglycolamide (TODGA), diluent hydrogenated tetrapropylene (TPH), and polar species water and nitric acid. We have also studied the effects of adding n-octanol and swapping TPH for n-dodecane. It would seem sensible to understand this simpler system before introducing metal complexes. Such an understanding would ideally arise from studying the system's properties over a wide range of compositions. The large number of components, however, precludes a comprehensive scan of compositions, so we have chosen to study a fixed concentration of TODGA while varying the concentrations of water and nitric acid over a substantial range. Reverse aggregates are observed, with polar species in the interior in contact with the polar portions of the TODGA molecules and the organic diluent on the exterior in contact with the TODGA alkyl chains. These aggregates are irregular in shape and grow in size as the amount of water and nitric acid increases. At a sufficiently high polar content, a single extended cluster forms corresponding to the third phase formation. No well-defined bonding motifs were observed between the polar species and TODGA. The cluster size distribution fits an isodesmic model, where the Gibbs energy change of adding a TODGA molecule to a cluster ranges between 4.5 and 7.0 kJ mol-1, depending on the system composition. The addition of n-octanol was found to reduce the degree of aggregation, with n-octanol acting as a co-surfactant. Exchanging the diluent TPH for n-dodecane also decreased the aggregation. We present evidence that this is due to the greater penetration of n-dodecane into the reverse aggregates. It is known, however, that the propensity for the third phase formation is greater with n-dodecane as the diluent than is the case with TPH, but we argue that these two results are not contradictory. This research casts light on the driving forces for aggregation, informs process engineers as to what species are present, and indicates that flow-sheet liquid-liquid extraction modeling might benefit by incorporating an isodesmic aggregation approach.

Theory and computer simulation for the cubatic phase of cut spheres.

The phase behavior of a system of hard-cut spheres has been studied using a high-order virial theory and by Monte Carlo simulation. The cut-sphere particles are disks of thickness L formed by symmetrically truncating the end caps of a sphere of diameter D . The virial theory predicts a stable nematic phase for aspect ratio LD=0.1 and a stable cubatic phase for LD=0.15-0.3 . The virial series converges rapidly on the equation of state of the isotropic and nematic phases, while for the cubatic phase the convergence is slower, but still gives good agreement with the simulation at high order. It is found that a high-order expansion (up to B8 ) is required to predict a stable cubatic phase for LD> or =0.15 , indicating the importance of many-body interactions in stabilizing this phase. Previous simulation work on this system has focused on aspect ratios LD=0.1 , 0.2, and 0.3. We expand this to include also LD=0.15 and 0.25, and we introduce a fourth-rank tensor to measure cubatic ordering. We have applied a multiparticle move which dramatically speeds the attainment of equilibrium in the nematic phase and therefore is of great benefit in the study of the isotropic-nematic phase transition. In agreement with the theory, our simulations confirm the stability of the nematic phase for LD=0.1 and the stability of the cubatic phase over the nematic for LD=0.15-0.3 . There is, however, some doubt about the stability of the cubatic phase with respect to the columnar. We have shown that the cubatic phase found on compression at LD=0.1 is definitely metastable, but the results for LD=0.2 were less conclusive.

A Telescoping View of Solute Architectures in a Complex Fluid System.

Short- and long-range correlations between solutes in solvents can influence the macroscopic chemistry and physical properties of solutions in ways that are not fully understood. The class of liquids known as complex (structured) fluids-containing multiscale aggregates resulting from weak self-assembly-are especially important in energy-relevant systems employed for a variety of chemical- and biological-based purification, separation, and catalytic processes. In these, solute (mass) transfer across liquid-liquid (water, oil) phase boundaries is the core function. Oftentimes the operational success of phase transfer chemistry is dependent upon the bulk fluid structures for which a common functional motif and an archetype aggregate is the micelle. In particular, there is an emerging consensus that mass transfer and bulk organic phase behaviors-notably the critical phenomenon of phase splitting-are impacted by the effects of micellar-like aggregates in water-in-oil microemulsions. In this study, we elucidate the microscopic structures and mesoscopic architectures of metal-, water-, and acid-loaded organic phases using a combination of X-ray and neutron experimentation as well as density functional theory and molecular dynamics simulations. The key conclusion is that the transfer of metal ions between an aqueous phase and an organic one involves the formation of small mononuclear clusters typical of metal-ligand coordination chemistry, at one extreme, in the organic phase, and their aggregation to multinuclear primary clusters that self-assemble to form even larger superclusters typical of supramolecular chemistry, at the other. Our metrical results add an orthogonal perspective to the energetics-based view of phase splitting in chemical separations known as the micellar model-founded upon the interpretation of small-angle neutron scattering data-with respect to a more general phase-space (gas-liquid) model of soft matter self-assembly and particle growth. The structure hierarchy observed in the aggregation of our quinary (zirconium nitrate-nitric acid-water-tri-n-butyl phosphate-n-octane) system is relevant to understanding solution phase transitions, in general, and the function of engineered fluids with metalloamphiphiles, in particular, for mass transfer applications, such as demixing in separation and synthesis in catalysis science.

Computer simulation and high level virial theory of Saturn-ring or UFO colloids.

Monte Carlo simulations are used to map out the complete phase diagram of hard body UFO systems, in which the particles are composed of a concentric sphere and thin disk. The equation of state and phase behavior are determined for a range of relative sizes of the sphere and disk. We show that for relatively large disks, nematic and solid phases are observed in addition to the isotropic fluid. For small disks, two different solid phases exist. For intermediate sizes, only a disordered fluid phase is observed. The positional and orientational structure of the various phases are examined. We also compare the equations of state and the nematic-isotropic coexistence densities with those predicted by an extended Onsager theory using virial coefficients up to B(8).

Structure of molecular liquids: hard rod-disk mixtures.

The structure of hard rod-disk mixtures is studied using Monte Carlo simulations and integral equation theory, for a range of densities in the isotropic phase. By extension of methods used in single component fluids, the pair correlation functions of the molecules are calculated and comparisons between simulation and integral equation theory, using a number of different closure relations, are made. Comparison is also made for thermodynamic data and phase behavior.

Structure and stability of isotropic states of hard platelet fluids.

We study the thermodynamics and the pair structure of hard, infinitely thin, circular platelets in the isotropic phase. Monte Carlo simulation results indicate a rich spatial structure of the spherical expansion components of the direct correlation function, including nonmonotonical variation of some of the components with density. Integral equation theory is shown to reproduce the main features observed in simulations. The hypernetted chain closure, as well as its extended versions that include the bridge function up to second and third order in density, perform better than both the Percus-Yevick closure and Verlet bridge function approximation. Using a recent fundamental measure density functional theory, an analytic expression for the direct correlation function is obtained as the sum of the Mayer bond and a term proportional to the density and the intersection length of two platelets. This is shown to give a reasonable estimate of the structure found in simulations, but to fail to capture the nonmonotonic variation with density. We also carry out a density functional stability analysis of the isotropic phase with respect to nematic ordering and show that the limiting density is consistent with that where the Kerr coefficient vanishes. As a reference system, we compare to simulation results for hard oblate spheroids with small, but nonzero elongations, demonstrating that the case of vanishingly thin platelets is approached smoothly.

Elastic constants of hard thin platelets by Monte Carlo simulation and virial expansion.

In this paper we present an investigation into the calculation of the Frank elastic constants of hard platelets via molecular simulation and virial expansion beyond second order. Monte Carlo simulations were carried out and director fluctuations measured as a function of wave vector k, giving the elastic constants through a fit in the low-k limit. Additionally, the virial expansion coefficients of the elastic constants up to sixth order were calculated, and the validity of the theory determined by comparison with the simulation results. The simulation results are also compared with experimental measurements on colloidal suspensions of platelike particles.

A Novel Microemulsion Phase Transition: Toward the Elucidation of Third-Phase Formation in Spent Nuclear Fuel Reprocessing.

We present evidence that the transition between organic and third phases, which can be observed in the plutonium uranium reduction extraction (PUREX) process at high metal loading, is an unusual transition between two isotropic bicontinuous microemulsion phases. As this system contains so many components, however, we have been seeking first to investigate the properties of a simpler system, namely, the related metal-free, quaternary water/n-dodecane/nitric acid/tributyl phosphate (TBP) system. This quaternary system has been shown to exhibit, under appropriate conditions, three coexisting phases: a light organic phase, an aqueous phase, and the so-called third phase. In the current work, we focused on the coexistence of the light organic phase with the third phase. Using Gibbs ensemble Monte Carlo (GEMC) simulations, we found coexistence of a phase rich in nitric acid and dilute in n-dodecane (the third phase) with a phase more dilute in nitric acid but rich in n-dodecane (the light organic phase). The compositions and densities of these two coexisting phases determined using the simulations were in good agreement with those determined experimentally. Because such systems are generally dense and the molecules involved are not simple, the particle exchange rate in their GEMC simulations can be rather low. To test whether a system having a composition between those of the observed third and organic phases is indeed unstable with respect to phase separation, we used the Bennett acceptance ratio method to calculate the Gibbs energies of the homogeneous phase and the weighted average of the two coexisting phases, where the compositions of these phases were taken both from experimental results and from the results of the GEMC simulations. Both demixed states were determined to have statistically significant lower Gibbs energies than the uniform, mixed phase, providing confirmation that the GEMC simulations correctly predicted the phase separation. Snapshots from the simulations and a cluster analysis of the organic and third phases revealed structures akin to bicontinuous microemulsion phases, with the polar species residing within a mesh and with the surface of the mesh formed by amphiphilic TBP molecules. The nonpolar n-dodecane molecules were observed in these snapshots to be outside this mesh. The only large-scale structural differences observed between the two phases were the dimensions of the mesh. Evidence for the correctness of these structures was provided by the results of small-angle X-ray scattering (SAXS) studies, where the profiles obtained for both the organic and third phases agreed well with those calculated from simulations. Finally, we looked at the microscopic structures of the two phases. In the organic phase, the basic motif was observed to be one nitric acid molecule hydrogen-bonded to a TBP molecule. In the third phase, the most common structure was that of the hydrogen-bonded TBP-HNO3-HNO3 chain. A cluster analysis provided evidence for TBP forming an extended, connected network in both phases. Studies of the effects of metal ions on these systems will be presented elsewhere.