Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Interfacial force modeling”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

72 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Elucidating Abnormal Grain Growth in Thermomagnetic Processed Materials with Transfer Learning and Reinforcement Learning

The goal of this research program is to establish the mechanism governing local grain boundary motion, which is needed to design and process desirable microstructures for better performance, by identifying the relative contributions of grain boundary (GB) energy and mobility to grain growth. Classical models for grain growth assume that the primary mechanism for reducing the total interfacial energy is area reduction and that GB restructuring is not significant. This assumption implies that grain growth is locally driven by curvature. However, recent experimental observations using new non-destructive 3D x-ray diffraction microscopy techniques (3D-XRM) reveal that classic descriptors (i.e., curvature, number of neighbors, grain size) do not predict real grain growth. Instead, local GB motion appears to be governed by its energy relative to its neighbors such that low-energy boundaries replace those of higher energy. However, simulations that incorporate GB energy anisotropy still fail to reproduce these observations. These discrepancies suggest that the common assumption for grain growth theory must be re-examined to predict and, thus, control microstructure evolution in real polycrystals. A significant challenge to testing this assumption is due to anisotropic GB mobility. Mobility may cause abnormal grain growth or affect the final grain shapes or growth rate but its true contributions are unknown because it is difficult to measure. For example, observations in Fe have found that grains associated with high energy and high mobility boundaries tend to experience abnormal grain growth, whereas abnormal grain growth is associated with low energy and high mobility boundaries in alumina. As mobility and energy both control GB motion, it is challenging to isolate the local driving forces necessary to test the common assumption that the primary mechanism is area reduction. The novelty of this work is the use of machine learning tools to capture GB mobility and energy from 3D-XRM measurements in polycrystals to test the common assumption used in grain growth models. Machine learning can capture high-order correlations in dynamic systems like those found in the evolving GB topology. The PIs have developed a physics-regularized interpretable machine learning microstructure evolution (PRIMME) model that accurately replicates the grain growth behavior of its trained data set.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Heterogeneous catalysis: Optimal performance at a phase boundary?

Most of the industrially used heterogeneous catalysts have been discovered by trial and error, and despite decades of experience, the discovery of new catalysts continues to be extremely challenging. The drive to uncover guiding principles in catalyst design is more present than ever. We share a series of observations indicating that optimal catalysts typically function at characteristic phase boundaries (e.g., abrupt changes in adsorbate coverage, catalyst structure, etc.) accessed in the reaction conditions. The catalyst exploits the associated instability—the desire to exist in multiple states simultaneously—as a driving force for chemical transformations. In other words, phase boundaries are good places to start the catalyst search, and indeed, we should focus on at least two phases at once rather than just one. Here, we substantiate this claim with several studies that combine statistical operando modeling and experiments. Transpiring from these observations is a hitherto unrecognized vector in catalyst discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Dynamic Surface Incorporation of Pb 2+ Ions at the Actively Dissolving Calcite (104) Surface

The reaction of dissolved Pb 2+ with calcite surfaces at near-equilibrium conditions involves adsorption of Pb 2+ and precipitation of secondary heteroepitaxial Pb-carbonate minerals. A more complex behavior is observed under far-from-equilibrium conditions, including strong inhibition of calcite dissolution, development of microtopography, and near-surface incorporation of multiple monolayers (ML) of Pb 2+ without precipitation of secondary phases [where 1 ML ≡ 1 Ca/20.2 Å 2 , the crystallographic site density of the calcite (104) lattice plane]. However, the mechanistic controls governing far-from-equilibrium reactivity are not well understood. Here, in this study, we observe the interfacial incorporation of dissolved Pb 2+ during the dissolution of calcite (104) surfaces at pH ~3.7 in a flow-through reaction cell, revealing the formation of a ~1 nm thick Pb-rich calcite layer with a total Pb coverage of ~1.4 ML. These observations of the sorbed Pb distribution used resonant anomalous X-ray reflectivity, X-ray fluorescence, and nanoinfrared atomic force microscopy. We propose that this altered surface layer represents a novel sorption mode that is stabilized by conditions of sustained disequilibrium. This behavior may significantly impact the transport of dissolved metals during disequilibrium processes occurring in acid mine drainage and subsurface CO 2 injection and, if appropriately accounted for, could improve the predictive capability of geochemical reactive-transport models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Surviving nanoscale interfacial stability in extreme thermal expansion contrast Zn(CN) 2 -epoxy resin matrix composites

Here, we report the remarkable stability at the nanoscale matrix-filler interface in a series of overall low coefficient of thermal expansion (CTE) zinc cyanide (ZC)/epoxy resin composites. These interfaces demonstrate the stability of highly contrasting materials. These composites are designed to optimize the properties of both materials: epoxy resins are valued for their high strength, superb chemical resistance, low dielectric properties, and adhesive abilities. ZC, a model flexible framework, exhibits negative thermal expansion (NTE) behavior and compensates for the epoxy resin’s detrimentally large thermal expansion values. Filled resins minimize the native 65 ppm/°C CTE values to 19 ppm/° C over a wide temperature range while maintaining linearity, yielding composites compatible with typical metal and ceramic substrates’—commonly bonded to the resin— 0–20 ppm/° C CTE values. Additionally, with significant intrinsic differences in the materials, we use wide-angle X-ray diffraction and atomic force microscopy to elucidate thermal movement. The ZC/epoxy interface is surprisingly resilient over 1,000 cycles between -55° C and 75° C, extremes typical to aerospace applications. Further, we show that the resin viscosity remains less than 21 Pa*s at up to 30 vol% ZC, an important consideration for workability. We also discuss settling distribution, glass transition temperature, flexural strength, and longevity. All results point favorably towards practical implementation in low thermal expansion application needs: filling the gap in component design.

42 ENGINEERING↗
DOE OSTI2025

Further Development of the Tamped Richtmyer-Meshkov Instability Method and Application to Molybdenum Dynamic Strength Calibration and Tabulation

The high pressure and high strain rate dynamic strength of Mo is experimentally and computationally investigated in the 3–20 GPa stress, 50–600 C temperature, and 10 5 –10 6 /s strain rate regimes using a modified tamped Richtmyer-Meshkov instability (RMI) method. Modifications to the tamped RMI method include a method to determine loading states during strain, a new strength calibration function based on interface shape, and a robust uncertainty quantification method. These modifications improve fidelity of the tamped RMI method, allowing evaluation of the compensating effects of pressure hardening, strain rate hardening, strain hardening, and thermal softening. The new calibration function based on interface shape is not limited to sinusoidal corrugations and could be applied to additional interface shapes. Plate impact experiments are performed at Argonne National Laboratory’s Advanced Photon Source’s Dynamic Compression Sector operated by Washington State University (DCS), driving a planar shock front through a corrugated Mo-D 2 O or Mo-C 8 F 18 interface, forcing the corrugation to significantly deform. The extent of interfacial deformation, RMI growth, is experimentally observed using X-ray phase contrast imaging at the DCS. RMI jet lengths and jet shapes are extracted from the experimental radiographs, then used to calibrate numerical simulations performed with the Sandia National Laboratories (SNL) hydrocode CTH. Mo yield strength, Y, as a function of shock pressure, P, strain rate, $\dot{\varepsilon }$, accumulated strain, ϵ, relative volumetric compression, RD , and temperature, T , is determined for each impact experiment and presented. The calibrated Mo yield strength values range 1.2–1.8 GPa, with strength generally decreasing as the impact stress increases. This trend is likely caused by thermal softening or strain localization. The tabular yield strength versus loading condition data presented in this paper can be used to fit complex strength models.

Voorhees, T. J. [Sandia National Lab. (SNL-CA), Li↗
DOE OSTI2023

Model for Humidity-Mediated Diffusion on Aluminum Surfaces and Its Role in Accelerating Atmospheric Aluminum Corrosion

Bare aluminum metal surfaces are highly reactive, which leads to the spontaneous formation of a protective oxide surface layer. Because many subsequent corrosive processes are mediated by water, the structure and dynamics of water at the oxide interface are anticipated to influence corrosion kinetics. Here, using molecular dynamics simulations with a reactive force field, we model the behavior of aqueous aluminum metal ions in water adsorbed onto aluminum oxide surfaces across a range of ion concentrations and water film thicknesses corresponding to increasing relative humidity. We find that the structure and diffusivity of both the water and the metal ions depend strongly on the humidity of the environment and the relative height within the adsorbed water film. Aqueous aluminum ion diffusion rates in water films corresponding to a typical indoor relative humidity of 30% are found to be more than 2 orders of magnitude slower than self-diffusion of water in the bulk limit. Connections between metal ion diffusivity and corrosion reaction kinetics are assessed parametrically with a reductionist model based on a 1D continuum reaction–diffusion equation. Our results highlight the importance of incorporating the properties specific to interfacial water in predictive models of aluminum corrosion.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Modeling Interactions within and between Peptide Amphiphile Supramolecular Filaments

Many peptides are able to self-assemble into one-dimensional (1D) nanostructures, such as cylindrical fibers or ribbons of variable widths, but the relationship between the morphology of 1D objects and their molecular structure is not well understood. Here, we use coarse-grained molecular dynamics (CG-MD) simulations to study the nanostructures formed by self-assembly of different peptide amphiphiles (PAs). The results show that ribbons are hierarchical superstructures formed by laterally assembled cylindrical fibers. Simulations starting from bilayer structures demonstrate the formation of filaments, whereas other simulations starting from filaments indicate varying degrees of interaction among them depending on chemical structure. These interactions are verified by observations using atomic force microscopy of the various systems. The interfilament interactions are predicted to be strongest in supramolecular assemblies that display hydrophilic groups on their surfaces, while those with hydrophobic ones are predicted to interact more weakly as confirmed by viscosity measurements. The simulations also suggest that peptide amphiphiles with hydrophobic termini bend to reduce their interfacial energy with water, which may explain why these systems do not collapse into superstructures of bundled filaments. The simulations suggest that future experiments will need to address mechanistic questions about the self-assembly of these systems into hierarchical structures, namely, the preformation of interactive filaments vs equilibration of large assemblies into superstructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Predicting interface structure using the minima hopping method

Here, we adapt the minima hopping method (MHM) to the problem of interfacial structure prediction and apply it to study a canonical problem, the tilt grain boundaries in SrTiO 3 . Our method employs a hybrid approach by first exploring the potential energy surface (PES) of different grain boundary samplings with an empirical force field, among which the fifteen candidates with lower energies are then refined using ab initio density functional theory (DFT) calculations. During the exploratory stage, we bias the search using a local order parameter to primarily sample various reconstructions in the vicinity of the interface, while preserving the crystallinity of the bulk regions. We further enhance the search by incorporating initial structures with rigid body displacements to account for translational variations between bulk phases, enabling the MHM to effectively generate both stoichiometric and nonstoichiometric SrTiO 3 Σ⁢3(111)[110] and Σ⁢3(112)[110] grain boundaries. From an algorithmic standpoint, MHM outperforms earlier studies based on genetic algorithms (GA) by identifying more stable interfacial structures of several SrTiO 3 grain boundaries. The performance of the present implementation of the MHM approach is primarily limited by exploring an approximate description of the PES with a rather simple Buckingham potential. This limitation leads to variations in performance when compared to approaches utilizing more advanced surrogate PES models, such as direct DFT-PES sampling or GA with the embedded atom method (EAM). Despite the present limitations, the MHM approach is able to yield interfacial structures with comparable or lower interfacial energies in specific cases, such as Σ⁢3(111)[110] Γ=1, ±0.5 and Σ⁢3(112)[110] Γ= ±1, −2, underscoring the robustness of the MHM approach even with a simple approximation of the DFT PES. The MHM interfacial structure prediction method thus offers an efficient approach to understanding the grain boundaries and heterointerfaces at the atomic scale, providing an important prerequisite for effective materials design.

density functional theory↗
DOE OSTI2021

In-plane quasi-single-domain BaTiO 3 via interfacial symmetry engineering

The control of the in-plane domain evolution in ferroelectric thin films is not only critical to understanding ferroelectric phenomena but also to enabling functional device fabrication. However, in-plane polarized ferroelectric thin films typically exhibit complicated multi-domain states, not desirable for optoelectronic device performance. Here we report a strategy combining interfacial symmetry engineering and anisotropic strain to design single-domain, in-plane polarized ferroelectric BaTiO 3 thin films. Theoretical calculations predict the key role of the BaTiO 3 /PrScO 3 (110) O substrate interfacial environment, where anisotropic strain, monoclinic distortions, and interfacial electrostatic potential stabilize a single-variant spontaneous polarization. A combination of scanning transmission electron microscopy, piezoresponse force microscopy, ferroelectric hysteresis loop measurements, and second harmonic generation measurements directly reveals the stabilization of the in-plane quasi-single-domain polarization state. This work offers design principles for engineering in-plane domains of ferroelectric oxide thin films, which is a prerequisite for high performance optoelectronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Nanometer Scale Imaging to Develop Quantitative Descriptors of Bipolar Membrane Junction Structure

Swings in pH can be achieved by electrically polarizing a bipolar membrane (BPM) to drive water dissociation at the BPM junction for electrochemical conversion and separation processes. BPM junction design is critical to tailor performance for specific applications; however, characterization techniques capable of resolving the nanometer scale physical structure of the junction are limited. We present sample preparation, imaging, and analysis workflows that are adaptable to a variety of BPM junction architectures. Atomic force microscopy produces BPM junction images with nanometer scale lateral resolution for samples with and without a graphene oxide water dissociation catalyst in the junction. Subsequent image segmentation and analysis quantify line edge roughness and catalyst layer thickness as descriptors of junction structure. Comparison of pre- and post-electrodialysis junctions suggests electric field-induced alignment of catalyst particles during electrodialysis. This characterization workflow can inform manufacturing protocols, computational modeling, and failure mode analysis for next-generation BPMs.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2026

Interface and Thermophysical Properties of R 32 Refrigerant

Driven by the urgent demand for efficient cooling in microelectronics and advanced thermal management systems, difluoromethane (R32/CH 2 F 2 ) has emerged as a promising candidate owing to its favorable thermophysical properties, including high heat transfer efficiency and low viscosity. While bulk properties such as density, viscosity, and thermal conductivity have been widely studied, interfacial properties, including surface tension and interfacial thickness, remain comparatively underexplored, despite their importance in phase-transition dynamics. Here, we perform molecular dynamics (MD) simulations from 180 to 300 K using an optimized transferable force field for fluoropropenes with enhanced electrostatics to assess both bulk and interfacial behavior of R32. Simulations reproduced density within ±2.1%, viscosity within 3.05%, and thermal conductivity within 7.41% of NIST reference data. Heat capacities (C p and C v ) were predicted within 5%. For interfacial properties, surface tension trends were reproduced within 13.58% deviation, and the vapor–liquid coexistence curve closely matched reference data, yielding a critical temperature of 345.7 K (1.6% deviation) and a critical density of 0.397 g/cm 3 (6.4% deviation). Importantly, the vapor–liquid interface exhibited pronounced temperature-dependent broadening across the 180–290 K range. This behavior correlates with increasing molecular kinetic energy, reduction in intermolecular cohesive interactions, and a progressive loss of preferential dipole alignment, which collectively enhance thermal fluctuation amplitudes at elevated temperatures. These validated results provide predictive molecular-level insights, particularly for interfacial properties that remain less characterized. By reducing property prediction errors in key parameters such as critical temperature, this work provides reliable inputs for heat-exchanger and system models. Such correlations can support optimized component sizing, improved performance, and reduced refrigerant charge. Beyond R32, the methodology offers a transferable framework for blended and next-generation low-GWP refrigerants, contributing to sustainable thermal management aligned with the 2027 EU F-Gas regulation and 2030 Kigali Amendment.

Fluids↗
DOE OSTI2023

A Deep Potential model for liquid–vapor equilibrium and cavitation rates of water

Computational studies of liquid water and its phase transition into vapor have traditionally been performed using classical water models. Here, we utilize the Deep Potential methodology—a machine learning approach—to study this ubiquitous phase transition, starting from the phase diagram in the liquid–vapor coexistence regime. The machine learning model is trained on ab initio energies and forces based on the SCAN density functional, which has been previously shown to reproduce solid phases and other properties of water. Here, we compute the surface tension, saturation pressure, and enthalpy of vaporization for a range of temperatures spanning from 300 to 600 K and evaluate the Deep Potential model performance against experimental results and the semiempirical TIP4P/2005 classical model. Moreover, by employing the seeding technique, we evaluate the free energy barrier and nucleation rate at negative pressures for the isotherm of 296.4 K. Further, we find that the nucleation rates obtained from the Deep Potential model deviate from those computed for the TIP4P/2005 water model due to an underestimation in the surface tension from the Deep Potential model. From analysis of the seeding simulations, we also evaluate the Tolman length for the Deep Potential water model, which is (0.091 ± 0.008) nm at 296.4 K. Finally, we identify that water molecules display a preferential orientation in the liquid–vapor interface, in which H atoms tend to point toward the vapor phase to maximize the enthalpic gain of interfacial molecules. We find that this behavior is more pronounced for planar interfaces than for the curved interfaces in bubbles. This work represents the first application of Deep Potential models to the study of liquid–vapor coexistence and water cavitation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Dynamic Barriers to Crystallization of Calcium Barium Carbonates

Metastable carbonates play important roles in geochemistry, biomineralization and serve as model systems for nonclassical theories of nucleation and growth. Balcite (Ca 0.5 Ba 0.5 CO 3 ) is a remarkable carbonate phase that is isostructural with a high-temperature modification of calcite (CaCO 3 ), yet can be synthesized at ambient conditions. Here, we investigate crystallization pathways in the Ba-Ca-CO 3 -H 2 O system, with a focus on the transformation of amorphous calcium barium carbonate (ACBC) to balcite and subsequent decomposition into the equilibrium calcite (CaCO3) and witherite (BaCO 3 ) phases. Density functional theory calculations show that balcite is an unstable solid solution (Ca 1-x BaxCO 3 , R 3¯ m) in the range 0.17 < x < 0.5, but is accessible through the amorphous ACBC precursor for x ≲ 0.5, and predict its decomposition into calcite and witherite. We confirm this pathway experimentally but found demixing to proceed slowly and remain incomplete even after 9 months. Nucleation kinetics of balcite from ACBC was assessed using a microfluidic assay, where increasing barium content led to a surprising increase in the balcite nucleation rate, despite decreasing thermodynamic driving force. We attribute crystallization rates that dramatically accelerate with time to changes in interfacial structure and composition during coarsening of the amorphous precipitate. By carefully quantifying the thermodynamic and kinetic contributions in the multistep crystallization of a metastable carbonate, we produce insights that allow us to better interpret the formation and persistence of metastable minerals in natural and synthetic environments.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Uptake of Pb and the Formation of Mixed (Ba,Pb)SO 4 Monolayers on Barite During Cyclic Exposure to Lead-Containing Sulfuric Acid

Barite (BaSO 4 ) is a common additive in lead-acid batteries, where it acts as a nucleating agent to promote the reversible formation and dissolution of PbSO 4 during battery cycling. However, little is known about the molecular-scale mechanisms the nucleation and cyclic evolution of PbSO 4 over a battery’s lifetime. In this study, we explore the responses of a barite (001) surface to cycles of high and low lead concentrations in the presence of 100 mM sulfuric acid using in-situ atomic force microscopy and high-resolution X-ray reflectivity. Here we find that PbSO 4 epitaxial films readily nucleate on the barite surface, even from solutions that are undersaturated relative to bulk PbSO 4 . Despite this, barite (001) proves to be an ineffective nucleator of bulk PbSO 4 , as multilayer growth is suppressed even in highly supersaturated solutions. Instead, we find evidence that Pb 2+ ions can directly exchange with Ba 2+ to create mixed (Ba,Pb)SO 4 surfaces. These chemically mixed surfaces do not host PbSO4 monolayers as readily as pristine barite, and the original reactivity is not regained until a fresh surface is reestablished by aggressive etching. Our results can be partly explained by traditional models of Stranski-Krastanov (S-K) growth, in which monolayer films are stabilized by a reduction in surface energy, but multilayer growth is inhibited by epitaxial strain. Complementary density functional theory calculations confirmed the basic energetic-terms of traditional S-K models, but also showed evidence form more complex, thickness-dependent, energetics than would be predicted from the S-K models. The experimental results can be better understood by extending the S-K model to consider the formation of mixed surfaces and films, which can have reduced strain and interfacial energies relative to pure films, while also being stabilized by entropy of mixing. These insights into non-stoichiometric heteroepitaxy will enable better predictions of how barite affects PbSO 4 nucleation in battery environments.

25 ENERGY STORAGE↗
DOE OSTI2024

Flow reversal benchmark of a one-sided heated narrow rectangular channel with CATHARE and RELAP5

Flow reversal in narrow coolant channels can be a crucial phenomenon for the safety of research reactors with a downward nominal flow direction. During a loss of forced flow accident, the downward flow stagnates briefly before transitioning into an upward natural circulation flow. The fuel may be damaged if dryout occurs and threshold fuel and/or cladding temperatures are exceeded. A comprehensive study is provided for flow reversal in narrow rectangular channels by examining experimental data and conducting software model analyses. The literature on flow reversal was reviewed, and selected experimental datasets were used to benchmark against CATHARE and RELAP5 models and also compare the code calculations with each other. The experimental data comes from flow reversal tests conducted with a narrow rectangular channel with one-sided heating. The results were compared with experimental data for successful flow reversal tests and predicted dryout power for dryout conditions. Also, the study examined the effects of the pump coastdown period, inlet liquid temperature, system pressure, and localized pressure drops. The experimental results showed that shorter coastdown periods, reduced pressure drops, and lower coolant inlet temperatures increased the dryout power. However, the system pressure did not noticeably affect the results. The simulation results showed that both CATHARE and RELAP5 agreed with experimental data, capturing the trends of the experimental results. Slight differences between each code calculation, as well as the predicted and measured dryout powers, were attributed to experimental uncertainties and the modeling of physical phenomena such as wall nucleation, interfacial heat transfer, drag coefficients, and critical heat flux. Overall, this study provides an understanding of flow reversal and the prediction capabilities of thermal-hydraulics software models. In conclusion, a future study of the flow reversal benchmark of a narrow rectangular channel with two-sided heating may provide additional valuable insights.

CATHARE↗
DOE OSTI2022

Particle-based hematite crystallization is invariant to initial particle morphology

Significance Many crystallization processes occurring in nature produce highly ordered hierarchical architectures. Their formation cannot be explained using classical models of monomer-by-monomer growth. One of the possible pathways involves crystallization through the attachment of oriented nanocrystals. Thus, it requires detailed understanding of the mechanism of particle dynamics that leads to their precise crystallographic alignment along specific faces. In this study, we discover a particle-morphology–independent oriented attachment mechanism for hematite nanocrystals. Independent of crystal morphology, particles always align along the [001] direction driven by aligning interactions between (001) faces and repulsive interactions between other pairs of hematite faces. These results highlight that strong face specificity along one crystallographic direction can render oriented attachment to be independent of initial particle morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Water–Hydrocarbon Interactions in Anionic Pyrene Monohydrate

Interactions between water and polycyclic aromatic hydrocarbons are essential in many aspects of chemistry, from interstellar and atmospheric processes to interfacial hydrophobicity and wetting phenomena. Despite their growing importance, the intermolecular potentials of the water-hydrocarbon interactions are underdeveloped compared to water-water potentials, and there are similarly few experimental probes that are sensitive to the details of the water-hydrocarbon potential. We present a combined experimental and computational study of anionic pyrene monohydrate, one of the simplest water/hydrocarbon clusters. The action spectrum in the OH region of the mass-selected cluster ion provides a rigorous benchmark for intermolecular potentials and computational methodologies. We identify missing intermolecular interactions and shortcomings in conventional dynamics calculations by comparing experimental data to density functional theory and classical molecular dynamics calculations. Kinetic trapping is prevalent, even for one water molecule and one pyrene molecule, leading to slow equilibration in conventional molecular dynamics calculations, even on nanosecond timescales and at low temperatures (50 K). At constant energy, temperature fluctuations for the pair of molecules are substantial. Immersing the system in a bath of soft spheres and employing parallel tempering alleviates kinetic trapping and dampens temperature fluctuations, bringing the system closer to the thermodynamic limit. With such augmented sampling, a simple, flexible water model reproduces the linewidth and the asymmetric broadening of the symmetric OH stretching mode, which we assign to spectral diffusion. In the OH stretching region, dynamics calculations predict a more intense antisymmetric peak than experiments observe but do not predict the bimodal split symmetric peak that the experiments show. Furthermore, our work suggests that electronic polarization, missing in the empirical force field, is responsible for the first discrepancy and that quantum nuclear effects, captured neither in density functional theory nor in classical dynamics, may be responsible for the second.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Surface Charge at an Oil/Water Interface Promoting the Enhancement and Assignment of Water Combination Bands

Given the different polarities and distinct chemical structures, it is no wonder that oil and water are incompatible neighbors. They can be forced to cooperate if provided sufficient energy or a suitable intermediary. Emulsions are the result of such a cooperation, where an emulsifying agent (the intermediary) in the form of a surfactant or a cocktail of surface stabilizing compounds allows for the ‘mixing’ of oil and water. Surfactant stabilized emulsions that are nanoscale in size (nanoemulsions) have caught the attention of many because of their newly discovered use in the synthesis of nanomaterials, oil recovery, drug delivery, and food science. Unlike smaller emulsions (e.g. microemulsions with 2-20 nm diameters), very little is known about the molecular level properties of nanoemulsions (NEs) whose diameters are in the 100-500 nm range. One thing that is well known is the macroscopic properties of droplets from these two size regimes are dramatically different, often for reasons not yet fully understood. Nanoemulsions do not form spontaneously and require an external shear beyond ordinary procedures used to create micelles. This shear is required to overcome the effects of surface tension and create droplets in the nanoscale regime. Once formed, however, they can be stable for long periods of time, making them very attractive for commercial and pharmaceutical products requiring a long shelf life. What is not well known is the interfacial molecular processes that lead to the formation and stability of nanoemulsions including those stabilized by surfactants and/or polymers. Such knowledge is important in understanding the molecular structure-function relationship that assists in predicting what additives and solvents are necessary for a specific application. Key to advancing nanoemulsion utility is to develop the needed molecular-level understanding of the structure and bonding interactions present at the surface of these soft nanoparticles.

36 MATERIALS SCIENCE↗