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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

An Accurate Potential Energy Surface for H2O

We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

Schwenke, David W.↗
NASA NTRS1998

A Comparison of ZnO and ZnO(-)

Ab initio electronic structure calculations are performed to support and to help interpret the experimental work reported in the proceeding manuscript. The CCSD(T) approach, in conjunction with a large basis set, is used to compute spectroscopic constants for the X(exp 1)Epsilon(+) and (3)II states of ZnO and the X(exp 2)Epsilon(+) state of ZnO(-). The spectroscopic constants, including the electron affinity, are in good agreement with experiment. The ZnO EA is significantly larger than that of O, thus relative to the atomic ground state asymptotes, ZnO(-) has a larger D(sub o) than the (1)Epsilon(+) state, despite the fact that the extra electron goes into an antibonding orbital. The changes in spectroscopic constants can be understood in terms of the X(exp 1)Epsilon(+) formally dissociating to Zn (1)S + O (1)D while the (3)II and (2)Epsilon(+) states dissociate to Zn (1)S + O (3)P and Zn (1) and O(-) (2)P, respectively.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1998

Modeling Intermolecular Interactions in Nanotubes, Fullerenes and Graphite using a New Long-Range Potential

The cohesive energy and compressibility of strands of a single-wall nanotube rope has been computed using a new long-range potential energy function derived from accurate ab initio quantum chemistry calculations of the benzene dimer and calibrated for energetic and mechanical properties of graphite (at pressures up to 12 GPa). We also use this potential to calculate a variety of properties of carbon nanotubes (both single- and multi-wall) and fullerenes. Extensive comparisons are made with previously published potentials.

Jaffe, Richard↗
NASA NTRS1988

A molecular orbital study of a model of the Mg2+ coordination complex of the self splicing reaction of ribosomal RNA

Recent discoveries have established the fact that RNA is capable of acting as an enzyme. In this study two different types of molecular orbital calculations, INDO and ab initio, were used in an attempt to assess the structural/functional role of the Mg2+ hydrated complex in ribozyme reactions. Preliminary studies indicate that the reaction is multistep and that the Mg2+ complex exerts a stabilizing effect on the intermediate or midpoint of the reaction.

Non-NASA Center↗
NASA NTRS2004

Modeling the interaction Between Ethylene Diamine and Water Films on the Surface of a Carbon Nanotube

It has been observed that a carbon nanotube (CNT) AFM tip coated with ethylene diamine (EDA) penetrates the liquid water-air interface more easily than an uncoated nanotube tip. The EDA coating remains intact through repeated cycles of dipping and removal. In order to understand the physical basis for this observation, we use ab initio quantum chemistry calculations to study the EDA-CNT-water interaction and to parameterize a force field describing this system. Molecular dynamics (MD) simulations are carried out for EDA-water mixtures and an EDA-coated carbon nanotube immmed in water. These simulations are similar to our earlier MD study that characterized the CNT-water interface. The attractive CNT-EDA and CNT-water interactions arise primarily from van der Waals forces, and the EDA-EDA, EDA-water and water-water interactions are mainly due to hydrogen bond formation. The binding energ of single EDA molecule to the nanotube is nearly three times larger than the corresponding value found for water (4.3 versus 1.5 kcal mol, respectively). The EDA molecules readily stick to and diffuse along the CNT surface. As a resulf mixing of the EDA and water films does not occur on the timescale of the MD simulations. The EDA film reduces the hydrophobicity of the nanotube surface and acts like a prototypical surfactant in stabilizing the suspension of carbon nanotubes in water. For this presentation, we use the MD simulations to determine how the presence of the carbon nanotube surface perturbs the properties of EDA-water mixtures.

Jaffe, Richard L.↗
NASA NTRS2014

Ab Initio Modeling of Molecular Radiation

Radiative emission from excited states of atoms and molecules can comprise a significant fraction of the total heat flux experienced by spacecraft during atmospheric entry at hypersonic speeds. For spacecraft with ablating heat shields, some of this radiative flux can be absorbed by molecular constituents in the boundary layer that are formed by the ablation process. Ab initio quantum mechanical calculations are carried out to predict the strengths of these emission and absorption processes. This talk will describe the methods used in these calculations using, as examples, the 4th positive emission bands of CO and the 1g+ 1u+ absorption in C3. The results of these calculations are being used as input to NASA radiation modeling codes like NeqAir, HARA and HyperRad.

spectroscopy↗
NASA NTRS2016

Collisional Dissociation of CO: ab initio Potential Energy Surfaces and Quasiclassical Trajectory Rate Coefficients

We have generated accurate global potential energy surfaces for CO+Ar and CO+O that correlate with atom-diatom pairs in their ground electronic states based on extensive ab initio electronic structure calculations and used these potentials in quasi-classical trajectory nuclear dynamics calculations to predict the thermal dissociation rate coefficients over 5000- 35000 K. Our results are not compatible with the 20-45 year old experimental results. For CO + Ar we obtain fairly good agreement with the experimental rate coefficients of Appleton et al. (1970) and Mick and Roth (1993), but our computed rate coefficients exhibit a stronger temperature dependence. For CO + O our dissociation rate coefficient is in close agreement with the value from the Park model, which is an empirical adjustment of older experimental results. However, we find the rate coefficient for CO + O is only 1.5 to 3.3 times larger than CO + Ar over the temperature range of the shock tube experiments (8000-15,000 K). The previously accepted value for this rate coefficient ratio is 15, independent of temperature. We also computed the rate coefficient for the CO + O ex- change reaction which forms C + O2. We find this reaction is much faster than previously believed and is the dominant process in the removal of CO at temperatures up to 16,000 K. As a result, the dissociation of CO is accomplished in two steps (react to form C+O2 and then O2 dissociates) that are endothermic by 6.1 and 5.1 eV, instead of one step that requires 11.2 eV to break the CO bond.

exchange rate coefficient↗
NASA NTRS2019

Thermodynamic Analysis of Boundary Layer Species During Ablation

The focus of this work is on carbon clusters, hydrocarbons and other carbonaceous species which are constituents of pyrolysis gases injected into the boundary layer. Some of these molecules are observed to have absorption spectra in the VUV and UV region that match the emission spectra of atomic nitrogen and oxygen. Hence, they can potentially absorb the radiation impinging on the heat shield. Accurate thermodynamic data is not available for many of these species over the relevant temperature range for reentry. The objective of this work is to determine the thermochemical properties of potential radiation absorbing molecules using accurate ab initio quantum chemistry calculations. We have compiled a database of formation enthalpies, anharmonic vibrational frequencies and rotational constants for the ground and low-lying excited electronic states of these carbonaceous species. Using these thermochemical properties, we compute equilibrium mole fractions and observe that the mole fractions of some species of interest are significant, thus they could affect the radiative heat flux. Furthermore, comparisons of the formation enthalpies and mole fractions are made with data from literature.

heatshields↗
NASA NTRSDate not supplied

A Holistic DSMC Transport Database for Re-Entry and Ablation Modeling

Hybrid simulation frameworks combining Computational Fluid Dynamics (CFD) and Direct Simulation Monte Carlo (DSMC) are frequently employed to efficiently perform high-fidelity solutions of environments containing combined continuum/rarified flow. The use of DSMC, a stochastic, particle-based method, is necessary for high-Knudsen flow where continuum-based assumptions governing CFD break down. However, the DSMC methodology is generally very computationally inefficient to model the continuum regime. In a CFD/DSMC hybrid approach, obtaining an accurate, high-fidelity solution hinges on the consistent treatment of transport properties and the used thermo-chemical models employed within the two solvers. In principle, in regions where CFD and DSMC are both employed, the same gas mixture under the same conditions should have the same properties, regardless of simulation type. Observed differences should be due to non-equilibrium processes, rather than differences in physical models. While the transport models governing CFD and DSMC simulations are starkly different, they can effectively be linked via their use of reduced Chapman-Enskog collision integrals. In CFD, these integrals are typically stored as fitted polynomial expressions and used to directly compute gas transport properties via mixing rules or the full Chapman-Enskog formulation. In DSMC, they can be used to derive the collision parameters needed for the phenomenological collision cross-section models that govern particle interactions, via a Nelder-Mead optimization scheme. The goal of this work is to provide a unified DSMC transport database encompassing the vast majority of known gas species encountered during atmospheric entry, on Earth or any other Solar body. This goal is largely possible due to recently performed ab-initio quantum chemistry calculations. Combined with other high-fidelity literature sources, the planned database will consist of collision integral data for over 200 neutral and ionized species and over 17000 binary collisions. From these collision integrals, Nelder-Mead optimization is used to compute Variable Soft Sphere (VSS) collision model parameters for DSMC, fitted from 300 K to 20000 K. Initial comparisons of transport properties of relevant equilibrium gas mixtures show great agreement between CFD and DSMC-derived results. The completed database will be able to be readily applied to model binary collisions of any gas mixture containing the included species over the specified temperature range, making it a valuable tool for future planetary probe modeling efforts. An example is shown below. Equilibrium mixture transport properties for a 19-species Titan atmospheric model [4] are computed using both fitted VSS parameters and the original CFD collision integral values. Deviations in computed properties between the two approaches is less than 5% for the entire temperature range.

M R Gosma↗
NASA NTRSDate not supplied

Predicting Melt Properties Using Atomistic Simulations With A Highly Accurate Physically Informed Neural Network Interatomic Potential

The use of a recently developed machine learning (ML) interatomic potential for molecular dynamics simulations of aluminum melt properties will be presented. Such properties are critical for process modeling in additive manufacturing, including the melt pool size, solidification, and formation of solidification microstructures. Direct first-principles modeling of these processes is computationally prohibitive whereas simulations employing ML potentials combine the high accuracy of quantum-mechanical methods with high computational speeds. The physically-informed neural network (PINN) method used herein, integrates a high-dimensional regression implemented by an artificial neural network with a physics-based bond-order interatomic potential. PINN potentials can accurately reproduce many properties of aluminum in both crystalline-solid and liquid phases. We examine the accuracy of a PINN Al potential in predicting the density, self-diffusivity, viscosity, and the tension of the liquid surface and liquid-solid interfaces. Comparison with experimental data and ab initio molecular dynamics calculations shows very good agreement for all properties tested.

molecular dynamics↗
NASA NTRSDate not supplied

Recommended DSMC Collision Model Parameters for Planetary Entry

Hybrid simulation frameworks combining Computational Fluid Dynamics (CFD) and Direct Simulation Monte Carlo (DSMC) are frequently employed to efficiently perform high-fidelity simulations of environments consisting of both continuum and rarified flow. DSMC is a stochastic, particle-based method which solves the fundamental Boltzmann equation and is therefore necessary for high-Knudsen flow where continuum-based assumptions governing CFD break down. However, the DSMC methodology is generally computationally inefficient to model the continuum regime. In a CFD/DSMC hybrid approach, obtaining an accurate, high-fidelity solution hinges on the consistent treatment of transport properties and the thermo-chemical models employed within the two solvers. In principle, in regions where CFD and DSMC are both employed, the same gas mixture under the same conditions should have the same properties, regardless of simulation type. Observed differences should be due to non-equilibrium processes, rather than differences in physical models. The goal of this work is to provide a comprehensive DSMC transport database encompassing the vast majority of known gas species encountered during Earth or other planetary atmospheric entry. This goal is largely possible due to recently performed ab initio quantum chemistry calculations. Combined with other high-fidelity data, the planned database will consist of collision integral data for over 200 neutral and ionized species and over 20000 binary collisions. From these collision integrals, Nelder-Mead optimization is used to compute collision-specific Variable Soft Sphere (VSS) collision model parameters, fitted from 300 K to 20000 K. Initial comparisons of transport properties of relevant equilibrium gas mixtures show great agreement between CFD and DSMC-derived results. The completed database can be readily applied to model binary collisions of any gas mixture containing the included species over the specified temperature range, making it a valuable tool for future planetary probe modeling efforts. An example is shown below in Fig. 1. Equilibrium mixture transport properties for a 35-species mixture composed originally of 10% air and 90% pyrolysis species of a carbon-phenolic ablator material [4] are computed using both fitted VSS Parameters and the original CFD collision integral values. Deviations in computed properties between the two approaches are less than 5% for the entire temperature range.

M. R. Gosma↗
NASA NTRS2002

Quantal Study of the Exchange Reaction for N + N2 using an ab initio Potential Energy Surface

The N + N2 exchange rate is calculated using a time-dependent quantum dynamics method on a newly determined ab initio potential energy surface (PES) for the ground A" state. This ab initio PES shows a double barrier feature in the interaction region with the barrier height at 47.2 kcal/mol, and a shallow well between these two barriers, with the minimum at 43.7 kcal/mol. A quantum dynamics wave packet calculation has been carried out using the fitted PES to compute the cumulative reaction probability for the exchange reaction of N + N2(J=O). The J - K shift method is then employed to obtain the rate constant for this reaction. The calculated rate constant is compared with experimental data and a recent quasi-classical calculation using a LEPS PES. Significant differences are found between the present and quasiclassical results. The present rate calculation is the first accurate 3D quantal dynamics study for N + N2 reaction system and the ab initio PES reported here is the first such surface for N3.

Wang, Dunyou↗
NASA NTRS1980

Vibration-rotation line shifts for 1 sigma g + H2/V,J/-1S/0/ He computed via close coupling - Temperature dependence

The density shifting of vibration-rotation transitions of H2 perturbed by He was computed (as a function of temperature) with no adjustable parameters. The calculation was carried out using the framework of the impact theory of Baranger with S-matrix elements obtained via close coupling calculations which incorporated the ab initio H2-H2 system potential of Tsapline et al.(1977). Vibrational and rotational inelasticity were neglected in the calculations; nevertheless good agreement with experimental data was obtained, up to moderate temperatures, for the density shift. A much poorer comparison was obtained for the density broadening.

Hahne, G. E.↗
NASA NTRS1999

Effective Forces Between Colloidal Particles

Colloidal suspensions have proven to be excellent model systems for the study of condensed matter and its phase behavior. Many of the properties of colloidal suspensions can be investigated with a systematic variation of the characteristics of the systems and, in addition, the energy, length and time scales associated with them allow for experimental probing of otherwise inaccessible regimes. The latter property also makes colloidal systems vulnerable to external influences such as gravity. Experiments performed in micro-ravity by Chaikin and Russell have been invaluable in extracting the true behavior of the systems without an external field. Weitz and Pusey intend to use mixtures of colloidal particles with additives such as polymers to induce aggregation and form weak, tenuous, highly disordered fractal structures that would be stable in the absence of gravitational forces. When dispersed in a polarizable medium, colloidal particles can ionize, emitting counterions into the solution. The standard interaction potential in these charged colloidal suspensions was first obtained by Derjaguin, Landau, Verwey and Overbeek. The DLVO potential is obtained in the mean-field linearized Poisson-Boltzmann approximation and thus has limited applicability. For more precise calculations, we have used ab initio density functional theory. In our model, colloidal particles are charged hard spheres, the counterions are described by a continuum density field and the solvent is treated as a homogeneous medium with a specified dielectric constant. We calculate the effective forces between charged colloidal particles by integrating over the solvent and counterion degrees of freedom, taking into account the direct interactions between the particles as well as particle-counterion, counterion-counterion Coulomb, counterion entropic and correlation contributions. We obtain the effective interaction potential between charged colloidal particles in different configurations. We evaluate two- and three-body forces in the bulk as well as study the influence of soft walls. We qualitatively explain the effects of the walls on the forces and demonstrate that many-body effects are negligible in our system. With adjustments in the parameters, the DLVO pair-potential can describe the results quantitatively. Besides electrostatic interactions, entropic depletion effects that arise from (hard-core) exclusion play an important role in determining the behavior of multi-component colloidal suspensions. A standard theory for depletion forces is due to Asakura and Oosawa and is based on the ideal gas approximation. To go beyond this approximation, we have studied entropic forces in molecular dynamics simulations of systems of hard spheres (the effects of the solvent have been ignored). The effective depletion forces for these systems can be found either from equilibrium distribution functions or from direct momentum transfer calculations. Our results obtained by either method show qualitative differences from the Asakura-Oosawa forces, indicating a longer range, higher value at contact and most importantly a more complicated structure, comprising of several maxima and minima. Our calculations include the determination of effective forces between two spheres, a hard sphere and a wall, and the behavior of a hard sphere near a step-edge and a corner. We also demonstrate that such entropic forces do not necessarily satisfy pairwise additivity.

Tehver, Riina↗
NASA NTRS1993

Structure and thermochemistry of ClO2 radicals

The structure of ClO2 has been calculated for the X 2A-double prime ground state using unrestricted Hartree-Fock (UHF), unrestricted second-order Moller-Plesset perturbation (UMP2), configuration interaction employing single and double excitation (CISD), and quadratic configuration interaction (QCI) ab initio molecular orbital methods. Calculations using UMP2 and CISD wave functions predict a ClO bond length of 1.728 +/- 0.01 A. The single-configuration-based QCI in the singles and doubles space with perturbation inclusion of triple substitutions, denoted QCISD(T), yield a ClO bond length of 2.205 A. The QCI results are consistent with results of Jensen (1990) who showed that the ClO bond length is 2.181 A using annihilated self-consistent methods (AUMP2). The thermochemistry of ClO2 radical has been calculated using MP2 and QCI methods employing an isodesmic scheme. Our scheme predicts the heat of formation for ClO2 at 0 K to be 24.6 +/- 2 kcal/mol.

Francisco, J. S.↗
NASA NTRS1994

Ab Initio Vibrational Levels For HO2 and Vibrational Splittings for Hydrogen Atom Transfer

We calculate vibrational levels and wave functions for HO2 using the recently reported ab initio potential energy surface of Walch and Duchovic. There is intramolecular hydrogen atom transfer when the hydrogen atom tunnels through a T-shaped saddle point separating two equivalent equilibrium geometries, and correspondingly, the energy levels are split. We focus on vibrational levels and wave functions with significant splitting. The first three vibrational levels with splitting greater than 2/cm are (15 0), (0 7 1) and (0 8 0) where V(sub 2) is the O-O-H bend quantum number. We discuss the dynamics of hydrogen atom transfer; in particular, the O-O distances at which hydrogen atom transfer is most probable for these vibrational levels. The material of the proposed presentation was reviewed and the technical content will not reveal any information not already in the public domain and will not give any foreign industry or government a competitive advantage.

Barclay, V. J.↗
NASA NTRS1973

Electron impact excitation and assignment of the low-lying electronic states of CO2

Electron scattering spectra of CO2 are reported in the 7 to 10 eV energy-loss range, at energies of 0.2, 0.35, 0.6, 0.7, and 7.0 eV above threshold, and at a scattering angle of 90 deg. Several new distinct overlapping continua with weak, diffuse bands superimposed are observed to lie in this energy-loss range. The experimental spectra are discussed in the light of recent ab initio configuration-interaction calculations of the vertical transition energies of CO2. The experimental spectra are shown to be consistent with the excitation states of CO2.

Hall, R. I.↗
NASA NTRS1975

Theoretical description of the 2A/double prime/ and 2A/prime/ states of the peroxyformyl radical

Simple orbital ideas are used to describe the lowest two states of the peroxyformyl radical, and ab initio Hartree-Fock calculations in these states are reported. It is found that both states may be formed exothermically by association of O2 and HCO in their ground states; however, the excited state may decompose readily to OH and CO2. The possible role of such processes in oxidation of aldelydes is discussed.

Winter, N. W.↗