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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.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Theoretical studies of a molecular beam generator

At present no adequate computer code exists for predicting the effects of thermal nonequilibrium on the flow quality of a converging-diverging N2 nozzle. It is the purpose of this research to develop such a code and then perform parametric studies to determine the effects of intermolecular forces (high gas pressure) and thermal nonequilibrium (the splitting of temperature into a vibrational and rotational-translational excitation) upon the flow quality. The two models to be compared are given. Appendix A contains nomenclature and additional relationships.

Heinbockel, John↗
NASA NTRS1971

Shock wave structure using nonlinear model Boltzmann equations

The structure of a strong plane shock wave in a monatomic rarefied perfect gas is one of the simplest problems able to be posed in kinetic theory, and one of the hardest to solve. Its simplicity lies in the absence of solid boundaries, geometrical complications, or internal molecular energy. Its difficulty arises from the great departure of the gas from equilibrium within the shock, which invalidates many of the techniques used successfully elsewhere in kinetic theory. In addition to this theoretical challenge, the modern development of ballistics and hypersonic flight has helped to stimulate extensive theoretical and experimental interest in the shock problem. The experimenters in turn have encountered great difficulties on account of the very small physical dimensions of shocks. In fact, until very recently indeed, any close comparisons of theoretical and experimental shock structure results have been rather unprofitable due to the inadequacies of both theory and experiment. During the last few years this situation has been appreciably improved by development of the Monte Carlo method. This allows idealized 'experiments' to be performed on large computers instead of in wind tunnels, using a known intermolecular force law. The most developed of these methods has been shown to be equivalent theoretically to the Boltzmann equation and to give results which agree extremely closely with measurements of high accuracy. Thus Monte Carlo results not only form the soundest basis for our present theoretical knowledge of shock wave structure, but, for purposes of developing other theories, can also be considered a very valuable experimental resource. However, such results remain very expensive to obtain. In this thesis we develop more economical kinetic theory methods for the approximate prediction of shock structure, and compare our results with those of the Monte Carlo method.

Segal, Ben Maurice↗
NASA NTRS1996

Cross-Effects in Microgravity Flows

Film growth by chemical/physical vapor deposition is a process of considerable interest in microgravity experiments. The absence of natural convection should allow better control of film growth processes but, in highly non-isothermal ampoules, thermal slip (creep) can become a matter of significant concern. The reported research is a theoretical and experimental investigation of the flow of gas/vapor mixtures under non-continuum conditions. The Boltzmann equation has been solved for a monatomic gas under non-condensing conditions and the various phenomenological coefficients have been computed. Computations for realistic potentials as well as for velocity and creep slip have been completed and the creep slip has been found to be dependent on the type of gas confirming the accuracy of previous variational results. The variational technique has been extended and planar flows calculated via the Burnett solutions. Velocity, diffusion and creep slips have been computed for gas mixtures and previously unknown dependencies of the creep slip on the mixture properties have been observed. Also for gas mixtures, an integral representation of the linearized Boltzmann operator has been developed for use in numerical and variational calculations for all intermolecular force laws. Two, two-bulb capillary systems have been designed, built and tested for the measurements of cross-flows; one of glass for isothermal measurements and one of stainless steel for non-isothermal measurements. Extensive data have been collected for Ar-He and N2-He mixtures at a variety of pressures and mole ratios. Viscosity, velocity slip coefficients and tangential momentum accommodation coefficients have been obtained from measurements with a spinning rotor gauge via a new theory that has been formulated for the spinning rotor gauge in the slip regime. The FIDAP fluid dynamics code has been applied to condensing flows in ampoules in the continuum regime and agreement obtained with the earlier work of Duval.

Loyalka, Sudarshan K.↗
NASA NTRS2001

Viscosity Coefficient Curve Fits for Ionized Gas Species Grant Palmer

Viscosity coefficient curve fits for neutral gas species are available from many sources. Many do a good job of reproducing experimental and computational chemistry data. The curve fits are usually expressed as a function of temperature only. This is consistent with the governing equations used to derive an expression for the neutral species viscosity coefficient. Ionized species pose a more complicated problem. They are subject to electrostatic as well as intermolecular forces. The electrostatic forces are affected by a shielding phenomenon where electrons shield the electrostatic forces of positively charged ions beyond a certain distance. The viscosity coefficient for an ionized gas species is a function of both temperature and local electron number density. Currently available curve fits for ionized gas species, such as those presented by Gupta/Yos, are a function of temperature only. What they did was to assume an electron number density. The problem is that the electron number density they assumed was unrealistically high. The purpose of this paper is two-fold. First, the proper expression for determining the viscosity coefficient of an ionized species as a function of both temperature and electron number density will be presented. Then curve fit coefficients will be developed using the more realistic assumption of an equilibrium electron number density. The results will be compared against previous curve fits and against highly accurate computational chemistry data.

Palmer, Grant↗
NASA NTRS2004

Theoretical and Experimental Investigation of the Stability of an Evaporating Constrained Vapor Bubble

The major accomplishments of the experimental portion of the research were documented in Ling Zheng's doctoral dissertation. Using Pentane, he obtained a considerable amount of data on the stability and heat transfer characteristics of an evaporating meniscus. The important points are that experimental equipment to obtain data on the stability and heat transfer characteristics of an evaporating meniscus were built and successfully operated. The data and subsequent analyses were accepted by the Journal of Heat Transfer for publication in 2004 [PU4]. The work was continued by a new graduate student using HFE-7000 [PU3] and then Pentane at lower heat fluxes. The Pentane results are being analyzed for publication. The experimental techniques are currently being used in our other NASA Grant. The oscillation of the contact line observed in the experiments involves evaporation (retraction part) and spreading. Since both processes occur with finite contact angles, it is important to derive a precise equation of the intermolecular forces (disjoining pressure) valid for non-zero contact angles. This theoretical derivation was accepted for publication by Journal of Fluid Mechanics [PU5]. The evaporation process near the contact line is complicated, and an idealized micro heat pipe has been proposed to help in elucidating the detailed evaporation process [manuscripts in preparation].

Wayner, P. C., Jr.↗
NASA NTRS2004

Microscale Investigation of Thermo-Fluid Transport in the Transition FIL, Region of an Evaporating Capillary Meniscus Using a Microgravity Environment

In order to enhance the fundamental understanding of thin film evaporation and thereby improve the critical design concept for two-phase heat transfer devices, microscale heat and mass transport is to be investigated for the transition film region using state-of-the-art optical diagnostic techniques. By utilizing a microgravity environment, the length scales of the transition film region can be extended sufficiently, from submicron to micron, to probe and measure the microscale transport fields which are affected by intermolecular forces. Extension of the thin film dimensions under microgravity will be achieved by using a conical evaporator made of a thin silicon substrate under which concentric and individually controlled micro-heaters are vapor-deposited to maintain either a constant surface temperature or a controlled temperature variation. Local heat transfer rates, required to maintain the desired wall temperature boundary condition, will be measured and recorded by the concentric thermoresistance heaters controlled by a Wheatstone bridge circuit, The proposed experiment employs a novel technique to maintain a constant liquid volume and liquid pressure in the capillary region of the evaporating meniscus so as to maintain quasi-stationary conditions during measurements on the transition film region. Alternating use of Fizeau interferometry via white and monochromatic light sources will measure the thin film slope and thickness variation, respectively. Molecular Fluorescence Tracking Velocimetry (MFTV), utilizing caged fluorophores of approximately 10-nm in size as seeding particles, will be used to measure the velocity profiles in the thin film region. An optical sectioning technique using confocal microscopy will allow submicron depthwise resolution for the velocity measurements within the film for thicknesses on the order of a few microns. Digital analysis of the fluorescence image-displacement PDFs, as described in the main proposal, can further enhance the depthwise resolution.

Kihm, K. D.↗
DOE OSTI2019

Analysis of the P-T and T-S phase boundary in discriminating suitable low global warming potential and low flammability refrigerants

Although several alternative low GWP refrigerants including natural have been proposed, the HVAC industry consensus on how to deal with the attendant issues is still evolving. This paper provides invaluable qualitative and quantitative insight into the peculiar phase boundary shapes of refrigerants, essential for understanding their application, and in evaluating existing and future refrigerants. The methodology is firmly grounded in the thermodynamics of phase equilibria and the criteria of positive-definiteness, a direct consequence of the Second Law and the existence of intermolecular forces (IMF). The formal methodology is strikingly easy to implement in practice and explains clearly why certain refrigerants display re-entrant behavior while others do not, and how one can choose the proper refrigerant for a given refrigeration or heat pump application. The paper shows how an evidence-based selection can be made among the 40 refrigerants analyzed in this study.

Ally, Moonis↗
DOE OSTI2019

Analysis of the P-T and T-S phase boundary in discriminating suitable low global warming potential and low flammability refrigerants

Although several alternative low GWP refrigerants including natural have been proposed, the HVAC industry consensus on how to deal with the attendant issues is still evolving. This paper provides a qualitative and quantitative insight into the peculiar phase boundary shapes of refrigerants, essential for understanding their application, and in evaluating existing and future refrigerants. The methodology is firmly grounded in the thermodynamics of phase equilibria and the criteria of positive-definiteness, a direct consequence of the Second Law and the existence of intermolecular forces (IMF). The formal methodology is strikingly easy to implement in practice and explains clearly why certain refrigerants display “re-entrant” behavior while others do not. The paper shows how an evidence-based selection can be made among the 40 refrigerants analyzed in this study. Keywords: Low GWP, alternate refrigerants, heat pumps, VLE

Ally, Moonis↗
DOE OSTI2016

Inter‐Fullerene Electronic Coupling Controls the Efficiency of Photoinduced Charge Generation in Organic Bulk Heterojunctions

Photoinduced charge generation (PCG) dynamics are notoriously difficult to correlate with specific molecular properties in device relevant polymer:fullerene organic photovoltaic blend films due to the highly complex nature of the solid state blend morphology. Here, this study uses six judiciously selected trifluoromethylfullerenes blended with the prototypical polymer poly(3‐hexylthiophene) and measure the PCG dynamics in 50 fs–500 ns time scales with time‐resolved microwave conductivity and femtosecond transient absorption spectroscopy. The isomeric purity and thorough chemical characterization of the fullerenes used in this study allow for a detailed correlation between molecular properties, driving force, local intermolecular electronic coupling and, ultimately, the efficiency of PCG yield. The findings show that the molecular design of the fullerene not only determines inter‐fullerene electronic coupling, but also influences the decay dynamics of free holes in the donor phase even when the polymer microstructure remains unchanged.

Larson, Bryon W.↗
DOE OSTI2020

On the origin of ground-state vacuum-field catalysis: Equilibrium consideration

Recent experiments suggest that vibrational strong coupling (VSC) may significantly modify ground-state chemical reactions and their rates even without external pumping. The intrinsic mechanism of this “vacuum-field catalysis” remains largely unclear. Generally, modifications of thermal reactions in the ground electronic states can be caused by equilibrium or non-equilibrium effects. The former are associated with modifications of the reactant equilibrium distribution as expressed by the transition state theory of chemical reaction rates, while the latter stem from the dynamics of reaching and leaving transition state configurations. In this work, we examine how VSC can affect chemical reactions rates in a cavity environment according to transition state theory. Our approach is to examine the effect of coupling to cavity mode(s) on the potential of mean force (PMF) associated with the reaction coordinate. Within the context of classical nuclei and classical photons and also assuming no charge overlap between molecules, we find that while the PMF can be affected by the cavity environment, this effect is negligible for the usual micron-length cavities used to examine VSC situations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A deep potential model with long-range electrostatic interactions

Machine learning models for the potential energy of multi-atomic systems, such as the deep potential (DP) model, make molecular simulations with the accuracy of quantum mechanical density functional theory possible at a cost only moderately higher than that of empirical force fields. However, the majority of these models lack explicit long-range interactions and fail to describe properties that derive from the Coulombic tail of the forces. To overcome this limitation, we extend the DP model by approximating the long-range electrostatic interaction between ions (nuclei + core electrons) and valence electrons with that of distributions of spherical Gaussian charges located at ionic and electronic sites. The latter are rigorously defined in terms of the centers of the maximally localized Wannier distributions, whose dependence on the local atomic environment is modeled accurately by a deep neural network. In the DP long-range (DPLR) model, the electrostatic energy of the Gaussian charge system is added to short-range interactions that are represented as in the standard DP model. The resulting potential energy surface is smooth and possesses analytical forces and virial. Missing effects in the standard DP scheme are recovered, improving on accuracy and predictive power. By including long-range electrostatics, DPLR correctly extrapolates to large systems the potential energy surface learned from quantum mechanical calculations on smaller systems. We illustrate the approach with three examples: the potential energy profile of the water dimer, the free energy of interaction of a water molecule with a liquid water slab, and the phonon dispersion curves of the NaCl crystal.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Secondary structure of rat and human amylin across force fields

The aggregation of human amylin has been strongly implicated in the progression of Type II diabetes. This 37-residue peptide forms a variety of secondary structures, including random coils, α-helices, and β-hairpins. The balance between these structures depends on the chemical environment, making amylin an ideal candidate to examine inherent biases in force fields. Rat amylin differs from human amylin by only 6 residues; however, it does not form fibrils. Therefore it provides a useful complement to human amylin in studies of the key events along the aggregation pathway. In this work, the free energy of rat and human amylin was determined as a function of α-helix and β-hairpin content for the Gromos96 53a6, OPLS-AA/L, CHARMM22/CMAP, CHARMM22*, Amberff99sb*-ILDN, and Amberff03w force fields using advanced sampling techniques, specifically bias exchange metadynamics. This work represents a first systematic attempt to evaluate the conformations and the corresponding free energy of a large, clinically relevant disordered peptide in solution across force fields. The NMR chemical shifts of rIAPP were calculated for each of the force fields using their respective free energy maps, allowing us to quantitatively assess their predictions. We show that the predicted distribution of secondary structures is sensitive to the choice of force-field: Gromos53a6 is biased towards β-hairpins, while CHARMM22/CMAP predicts structures that are overly α-helical. OPLS-AA/L favors disordered structures. Amberff99sb*-ILDN, AmberFF03w and CHARMM22* provide the balance between secondary structures that is most consistent with available experimental data. In contrast to previous reports, our findings suggest that the equilibrium conformations of human and rat amylin are remarkably similar, but that subtle differences arise in transient alpha-helical and beta-strand containing structures that the human peptide can more readily adopt. We hypothesize that these transient states enable dynamic pathways that facilitate the formation of aggregates and, eventually, amyloid fibrils.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Proton radiation effects in indium oxide using cascade molecular dynamics simulations

Metal oxide (MO) semiconductors, characterized by their wide band gaps and notable charge transport properties, are promising candidates for electronic applications in extreme environments, including near-Earth space. However, atomistic simulations of radiation–matter interactions in MOs remain challenging due to the limitations of existing interatomic potentials, which often fail to capture both the short-range repulsive forces essential for radiation damage modeling and the long-range electrostatic effects governing defect evolution. In this work, we develop a customized interatomic potential tailored for radiation damage simulations in indium oxide (In 2 O 3 ) as a model system, a representative MO material. Our potential integrates the Ziegler-Biersack-Littmark potential to accurately describe short-range interactions with Buckingham and Coulombic potentials to account for long-range forces. We perform molecular dynamics simulations of low-energy proton irradiation using this custom potential. We employ the primary knock-on atom (PKA) cascade method to study atomic displacements and primary defect formation. Simulations were conducted for 1 keV proton irradiation in four randomly chosen directions, and PKA-driven defect analyses at 5, 10, and 15 keV to examine the effects of direction and energy level on damage generation. Our results provide insight into the impact of irradiation direction and energy level on the cascade evolution and defect formation mechanisms.

Atomistic simulations↗
DOE OSTI2019

Formation of Hierarchical Architectures with Dimensional and Morphological Control in the Self‐Assembly of Conjugated Block Copolymers

Abstract Precise control of dimensionality and morphology is a crucial requirement for realizing complex and hierarchical assembled structures, which has mainly been studied in highly crystalline systems. However, such results have rarely been reported in the self‐assembly of conjugated block copolymers with relatively weak π–π interactions. Herein, the realization of unique scarf‐like self‐assembled architectures based on the conjugated block copolymers through a facile one‐step approach is reported. Dimensional and morphological control of the micelles are realized by adjusting the block ratio and the solvent polarity. Then the transformation from 1D nanorods to the final hierarchical scarf micelles is observed. Furthermore, the underlying growth mechanism is mainly attributed to the driving force of intermolecular π–π interactions between conjugated core blocks. This work provides a highly effective strategy to prepare hierarchical architectures circumventing those multistep methods used in traditional crystallization system, which could expand the morphological diversity of self‐assembly and further facilitate the exploration of its functional applications.

Wang, Meijing↗
DOE OSTI2014

When do we need attractive-repulsive intermolecular potentials?

The role of attractive-repulsive interactions in direct simulation Monte Carlo (DSMC) simulations is studied by comparing with traditional purely repulsive interactions. The larger collision cross section of the long-range LJ potential is shown to result in a higher collision frequency and hence a lower mean free path, by at least a factor of two, for given conditions. This results in a faster relaxation to equilibrium as is shown by comparing the fourth and sixth moments of the molecular velocity distribution obtained using 0-D DSMC simulations. A 1-D Fourier-Couette flow with a large temperature and velocity difference between the walls is used to show that matching transport properties will result in identical solutions using both LJPA and VSS models in the near-continuum regime. However, flows in the transitional regime with Knudsen number, Kn ∼ 0.5 show a dependence on the intermolecular potential in spite of matching the viscosity coefficient due to differences in the collision frequency. Attractive-repulsive potentials should be used when both transport coefficients and collision frequencies should be matched.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Chemical gas-dynamics beyond Wang Chang-Uhlenbeck's kinetics

Wang Chang-Uhlenbeck equation does not give possibility to take into account intermolecular processes such as redistribution of the energy among different degrees of freedom. The modification of the generalized Wang Chang-Uhlenbeck equation including such processes is proposed. It allows to study for instance the kinetics of non-radiative transitions. Limitations of this approach are connected with the requirements of absence of polarization of rotational momentum and phases of intermolecular vibrations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Three-dimensional potential energy surface of Ar–CO

A three-dimensional intermolecular potential energy surface of the Ar–CO complex has been determined by fitting most of the previously reported spectroscopic data, where observed transition frequencies by microwave, millimeter-wave, submillimeter-wave, and infrared spectroscopy were reproduced simultaneously within their experimental accuracies. A free rotor model Hamiltonian considering all the freedom of motions for an atom-diatom system was applied to calculate vibration-rotation energies. A three-dimensional potential energy surface obtained by ab initio calculations at the CCSD(T)-F12b/aug-cc-pV5Z level of theory was parameterized by a model function consisting of 46 parameters. They were used as initial values for the least-squares analysis of the experimental data. A total of 20 parameters were optimized to reproduce all the spectroscopic data.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Anomalous hole injection deterioration of organic light-emitting diodes with a manganese phthalocyanine layer

Metal phthalocyanines (MPcs) are well known as an efficient hole injection layer (HIL) in organic devices. They possess a low ionization energy, and so the low-lying highest occupied molecular orbital (HOMO) gives a small hole injection barrier from an anode in organic light-emitting diodes. However, in this study, we show that the hole injection characteristics of MPc are not only determined by the HOMO position but also significantly affected by the wave function distribution of the HOMO. We show that even with the HOMO level of a manganese phthalocyanine (MnPc) HIL located between the Fermi level of an indium tin oxide anode and the HOMO level of a N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine hole transport layer the device performance with the MnPc HIL is rather deteriorated. This anomalous hole injection deterioration is due to the contracted HOMO wave function, which leads to small intermolecular electronic coupling. The origin of this contraction is the significant contribution of the Mn d-orbital to the MnPc HOMO.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗