Search NASA⌕ Search

SEARCH · Search NASA

Results for “ab initio calculations”

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.

At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
NASA NTRS2007

Theoretical Studies of Routes to Synthesis of Tetrahedral N4

A paper [Chem. Phys. Lett. 345, 295 (2001)] describes theoretical studies of excited electronic states of nitrogen molecules, with a view toward utilizing those states in synthesizing tetrahedral N4, or Td N4 a metastable substance under consideration as a high-energy-density rocket fuel. Several ab initio theoretical approaches were followed in these studies, including complete active space self-consistent field (CASSCF), state-averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD). Standard double zeta polarized and triple zeta double polarized one-particle basis sets were used. The CASSCF calculations overestimated the excitation energies, while SACASSCF calculations partly corrected these overestimates. The accuracy of the CIS calculations varied, depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results were in generally good agreement. The energies of the lowest six excited singlet states of Td N4 as calculated by the LRCCSD were compared with the energies of possible excited states of N2 + N2 fragments, leading to the conclusion that the most likely route for synthesis of Td N4 would involve a combination of two bound quintet states of N2.

Lee, Timothy J.↗
NASA NTRS1987

Vibration-rotational intensities for the X 1Sigma(+) state of A1H and A1D

In the present calculation of vibrational-rotational line strengths for the ground electronic state of A1H and A1D, the vibrational and rotational quantum numbers used are respectively in the Delta-v zero-5 range for v-prime between zero and 15, and J-prime-J of + or - 1 for J-prime in the zero-50 range. The transition matrix elements were obtained on the basis of the Meyer and Rosmus (1975) ab initio dipole-moment function, together with the numerical vibrational-rotational energy function.

Tipping, R. H.↗
NASA NTRS2013

High-Accuracy Quartic Force Field Calculations for the Spectroscopic Constants and Vibrational Frequencies of 1(exp 1)A' l-C3H(-): A Possible Link to Lines Observed in the Horsehead Nebula PDR

It has been shown that rotational lines observed in the Horsehead nebula photon-dominated-region (PDR) are probably not caused by l-C3H+, as was originally suggested. In the search for viable alternative candidate carriers, quartic force fields are employed here to provide highly accurate rotational constants, as well as fundamental vibrational frequencies, for another candidate carrier: 1 (sup 1)A' C3H(−). The ab initio computed spectroscopic constants provided in this work are, compared to those necessary to define the observed lines, as accurate as the computed spectroscopic constants for many of the known interstellar anions. Additionally, the computed D-eff for C3H(−) is three times closer to the D deduced from the observed Horsehead nebula lines relative to l-C3H(+). As a result, 1 (sup 1)A' C3H(−). is a more viable candidate for these observed rotational transitions and would be the seventh confirmed interstellar anion detected within the past decade and the first C(sub n)H(−) molecular anion with an odd n.

Horsehead nebula↗
NASA NTRS2005

Rare Gases Inserted into Biological Building Blocks: A Theoretical Study of Glycine - Rg Compounds (Rg-Xe, Kr, Ar)

Compounds formed by insertion of rare-gas atoms (Xe, Kr, and Ar) into glycine molecule are investigated using accurate ab initio computational methods. Identification of such insertion compounds may open new frontiers in the field of rare-gas chemistry, such as possible existence of biological molecules that include chemically bound rare gas atoms. The most stable glycine-Rg configuration is found to correspond to insertion of Rg atoms into the 0-H bond of glycine. These NH2CH2COORgH compounds are metastable , but separated by sizable potential barriers from the Rg + glycine dissociation products. Preliminary calculations show that NH2CH2COOXeH compound is energetically stable with respect to another (3-body) dissociation channel (NH2CH2COO + Rg + H), while the corresponding Ar species is not stable in this respect. The compound with the inserted Kr is a borderline case, with the 3-body dissociation products being close in energy to the NH2CH2COOKrH minimum.

Chaban, Galina M.↗
NASA NTRS2018

Calculation of Thermochemical Properties of Carbon-cluster Ablation Species

Carbon clusters and hydrocarbons are constituents of the pyrolysis gases injected into the boundary layer of a space vehicle with a carbonaceous heat shield. These molecules 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 of the space vehicle. This paper studies the ground state thermochemical properties and low-lying excited electronic states of potential radiation absorbing molecules present in the boundary layer using ab initio quantum chemistry methods. These results provide a more accurate prediction of the radiative heat flux on the surface which can lead to improvement in the design of the thermal protection system.

enthalpy↗
NASA NTRS2001

Theoretical Studies of Possible Synthetic Routes for the High Energy Density Material Td N4: Excited Electronic States

Vertical electronic excitation energies for single states have been computed for the high energy density material (HEDM) Td N4 in order to assess possible synthetic routes that originate from excited electronic states of N2 molecules. Several ab initio theoretical approaches have been used, including complete active space self-consistent field (CASSCF), state averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D)) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD), which is the highest level of theory employed. Standard double zeta polarized (DZP) and triple zeta double polarized (TZ2P) one-particle basis sets were used. The CASSCF calculations are found to overestimate the excitation energies, while the SA-CASSCF approach rectifies this error to some extent, but not completely. The accuracy of the CIS calculations varied depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results are in generally good agreement. Based on the LRCCSD calculations, the lowest six excited singlet states are 9.35(l(sup)T1), 10.01(l(sup)T2), 10.04(1(sup)A2), 10.07(1(sup)E), 10.12(2(sup)T1), and 10.42(2(sup)T2) eV above the ground state, respectively. Comparison of these excited state energies with the energies of possible excited states of N2+N2 fragments, leads us to propose that the most likely synthetic route for Td N4 involving this mechanism arises from combination of two bound quintet states of N2.

Lee, Timothy J.↗
NASA NTRS2014

Realistic Modeling of Multi-Scale MHD Dynamics of the Solar Atmosphere

Realistic 3D radiative MHD simulations open new perspectives for understanding the turbulent dynamics of the solar surface, its coupling to the atmosphere, and the physical mechanisms of generation and transport of non-thermal energy. Traditionally, plasma eruptions and wave phenomena in the solar atmosphere are modeled by prescribing artificial driving mechanisms using magnetic or gas pressure forces that might arise from magnetic field emergence or reconnection instabilities. In contrast, our 'ab initio' simulations provide a realistic description of solar dynamics naturally driven by solar energy flow. By simulating the upper convection zone and the solar atmosphere, we can investigate in detail the physical processes of turbulent magnetoconvection, generation and amplification of magnetic fields, excitation of MHD waves, and plasma eruptions. We present recent simulation results of the multi-scale dynamics of quiet-Sun regions, and energetic effects in the atmosphere and compare with observations. For the comparisons we calculate synthetic spectro-polarimetric data to model observational data of SDO, Hinode, and New Solar Telescope.

Realistic Modeling↗
NASA NTRS1996

Quantum Mechanical Determination of Potential Energy Surfaces for TiO and H2O

We discuss current ab initio methods for determining potential energy surfaces, in relation to the TiO and H2O molecules, both of which make important contributions to the opacity of oxygen-rich stars. For the TiO molecule we discuss the determination of the radiative lifetimes of the excited states and band oscillator strengths for both the triplet and singlet band systems. While the theoretical radiative lifetimes for TiO agree well with recent measurements, the band oscillator strengths differ significantly from those currently employed in opacity calculations. For the H2O molecule we discuss the current results for the potential energy and dipole moment ground state surfaces generated at NASA Ames. We show that it is necessary to account for such effects as core-valence Correlation energy to generate a PES of near spectroscopic accuracy. We also describe how we solve the ro-vibrational problem to obtain the line positions and intensities that are needed for opacity sampling.

Langhoff, Stephen R.↗
NASA NTRS1975

Phenomenological treatments of cross-sections for proton and hydrogen impact below 1 keV on molecular nitrogen

An analytic independent-particle model is used to construct static potentials to describe the interaction of hydrogen-like ions with atoms and molecules. Parameters of the ion-atom potential are determined from ab initio total energy minimization procedure. The elastic scattering of He(+) from Ne and Ar is investigated as a test case and comparison is made with experiment. The model is then used in conjunction with low energy H(+)-N2 experimental data to construct differential and total cross-sections for the scattering of protons and hydrogen in the energy range of 10 eV to 1 keV from molecular nitrogen. Analytic forms are used to parametrize these cross-sections to facilitate their use in the calculation of energy deposition by protons and hydrogen atoms in atmospheric gases.

Porter, H. S.↗
NASA NTRS1992

An extensive ab initio study of the structures, vibrational spectra, quadratic force fields, and relative energetics of three isomers of Cl2O2

Quantum mechanical computational methods are employed for an ab initio investigation of: (1) the molecular properties of the lowest isomers of the ClO dimer; and (2) predicted molecular and thermochemical properties. Techniques employed include electron correlation and particularly singles and doubles coupled-cluster (CCSD) theory with or without perturbational estimates of the effects of connected triple excitations. The isomers ClOClO and ClClO2 are found to have higher energies than the ClOOCl isomer, and the theoretical vibrational frequencies of the isomers are well correlated with experimental data. Experimental values of the heat of formation for the isomers are also compared with calculations based on an isodesmic reaction with Cl2O, H2O, and HOOH.

Lee, Timothy J.↗
NASA NTRS2003

Heats of Segregation of BCC Metals Using Ab Initio and Quantum Approximate Methods

Many multicomponent alloys exhibit surface segregation, in which the composition at or near a surface may be substantially different from that of the bulk. A number of phenomenological explanations for this tendency have been suggested, involving, among other things, differences among the components' surface energies, molar volumes, and heats of solution. From a theoretical standpoint, the complexity of the problem has precluded a simple, unified explanation, thus preventing the development of computational tools that would enable the identification of the driving mechanisms for segregation. In that context, we investigate the problem of surface segregation in a variety of bcc metal alloys by computing dilute-limit heats of segregation using both the quantum-approximate energy method of Bozzolo, Ferrante and Smith (BFS), and all-electron density functional theory. In addition, the composition dependence of the heats of segregation is investigated using a BFS-based Monte Carlo procedure, and, for selected cases of interest, density functional calculations. Results are discussed in the context of a simple picture that describes segregation behavior as the result of a competition between size mismatch and alloying effects

Good, Brian↗
NASA NTRS2022

Recommended Direct Simulation Monte Carlo Collision Model Parameters for Reacting Methane Flows

While hydrocarbon combustion and gas-surface interactions have been simulated for a variety of applications in continuum solvers, such processes have been rarely investigated in Direct Simulation Monte Carlo (DSMC). Thus Variable Hard/Soft Sphere (VHS/VSS)collision parameters are not available for most molecules of interest in the decomposition of methane, a significant pyrolysis gas product and potential atmospheric species for Titan re-entries. As these properties are essential for accurate modeling of gas transport and thermochemical effects, a method must be devised to compute them for use in DSMC. In this study, the methodology outlined in Stephani et al is utilized to compute the VHS/VSS parameters by fitting the Ω(1,1)and Ω(2,2) collision integrals [1]. These collision integrals are typically computed from intermolecular potentials and are used in CFD simulations to calculate transport properties such as viscosity, thermal conductivity, and diffusion. This approach ensures consistency between micro-scale collisions and macro-scale transport properties. To produce the necessary collision integrals needed for the fitting routine, we utilize the method described by Laricchiuta et al, where collision integrals are computed based on the constituent particles’ polarizability and effective electron number [2].Preliminary computations of pure-species Ω(1,1)and Ω(2,2)collision integrals produced from the coupled approach of Stephani et al and Laricchiuta et al for methane show good agreement with those computed via available ab-initio Potential Energy Surface Computations, as seen in Figure 1. Above 300K, no more than 12% deviation is observed between the two results over the temperature range of the fitted PES data [3].Current results of this study include full collision-specificVSS transport properties for a complex-species mixture involving major byproducts of pure methane decomposition. Targeted final results will include a comprehensive list of VSS parameters relevant toDSMC simulations of Titan atmospheric entry, based on the reduced kinetic model of Savajano et al [4].

M R Gosma↗
NASA NTRS1992

Calculations of ion-molecule deuterium fractionation reactions involving HD

Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.

Maluendes, Sergio A.↗
NASA NTRS2004

adwTools Developed: New Bulk Alloy and Surface Analysis Software for the Alloy Design Workbench

A suite of atomistic modeling software, called the Alloy Design Workbench, has been developed by the Computational Materials Group at the NASA Glenn Research Center and the Ohio Aerospace Institute (OAI). The main goal of this software is to guide and augment experimental materials research and development efforts by creating powerful, yet intuitive, software that combines a graphical user interface with an operating code suitable for real-time atomistic simulations of multicomponent alloy systems. Targeted for experimentalists, the interface is straightforward and requires minimum knowledge of the underlying theory, allowing researchers to focus on the scientific aspects of the work. The centerpiece of the Alloy Design Workbench suite is the adwTools module, which concentrates on the atomistic analysis of surfaces and bulk alloys containing an arbitrary number of elements. An additional module, adwParams, handles ab initio input for the parameterization used in adwTools. Future modules planned for the suite include adwSeg, which will provide numerical predictions for segregation profiles to alloy surfaces and interfaces, and adwReport, which will serve as a window into the database, providing public access to the parameterization data and a repository where users can submit their own findings from the rest of the suite. The entire suite is designed to run on desktop-scale computers. The adwTools module incorporates a custom OAI/Glenn-developed Fortran code based on the BFS (Bozzolo- Ferrante-Smith) method for alloys, ref. 1). The heart of the suite, this code is used to calculate the energetics of different compositions and configurations of atoms.

Bozzolo, Guillermo↗
NASA NTRSDate not supplied

Downfolding Complex Materials Problems Onto Model Hamiltonians for Quantum Computers

Simulating the properties of quantum materials is expected to be one of the exciting applications for quantum computers and where we hope to see advantages over classical hardware. The complexity of ab initio Hamiltonians describing the physics of application-relevant materials places them beyond the realm of possibility for solution on near-term hardware with a limited number of qubits. Various Hamiltonian approximations, including Hamiltonian downfolding, offers a possibility towards simulating complex materials on near-term hardware. This is accomplished by approximating the relevant physics of a given material through their representation by simpler model Hamiltonians, such as the Hubbard Hamiltonian or extensions of it. Here we employ a well-defined first-principles methodology for deriving downfolded multi-band extended Hubbard Hamiltonians of materials, capturing strong electronic correlation and electron-phonon coupling, based on the formalism of Wannier functions and the calculation of the screened Coulomb interaction. We demonstrate for a variety of systems that quantum simulation of these downfolded Hamiltonians reproduces key properties, thus establishing downfolding as a promising route to achieve near-term simulation of application-relevant systems on quantum hardware.

Antonios Markos Alvertis↗
NASA NTRSDate not supplied

Downfolding complex materials problems onto model Hamiltonians for quantum computers

Simulating the properties of quantum materials is expected to be one of the exciting applications for quantum computers and where we hope to see advantages over classical hardware. The complexity of ab initio Hamiltonians describing the physics of application-relevant materials places them beyond the realm of possibility for solution on near-term hardware with a limited number of qubits. Various Hamiltonian approximations, including Hamiltonian downfolding, offers a possibility towards simulating complex materials on near-term hardware. This is accomplished by approximating the relevant physics of a given material through their representation by simpler model Hamiltonians, such as the Hubbard Hamiltonian or extensions of it. Here we employ a well-defined first-principles methodology for deriving downfolded multi-band extended Hubbard Hamiltonians of materials, capturing strong electronic correlation and electron-phonon coupling, based on the formalism of Wannier functions and the calculation of the screened Coulomb interaction. We demonstrate for a variety of systems that quantum simulation of these downfolded Hamiltonians reproduces key properties, thus establishing downfolding as a promising route to achieve near-term simulation of application-relevant systems on quantum hardware.

Antonios M. Alvertis↗
NASA NTRS1989

The dissociation energy of N2

The requirements for very accurate ab initio quantum chemical prediction of dissociation energies are examined using a detailed investigation of the nitrogen molecule. Although agreement with experiment to within 1 kcal/mol is not achieved even with the most elaborate multireference CI (configuration interaction) wave functions and largest basis sets currently feasible, it is possible to obtain agreement to within about 2 kcal/mol, or 1 percent of the dissociation energy. At this level it is necessary to account for core-valence correlation effects and to include up to h-type functions in the basis. The effect of i-type functions, the use of different reference configuration spaces, and basis set superposition error were also investigated. After discussing these results, the remaining sources of error in our best calculations are examined.

Almloef, Jan↗
NASA NTRS1989

The dissociation energy of N2

The requirements for very accurate ab initio quantum chemical prediction of dissociation energies are examined using a detailed investigation of the nitrogen molecule. Although agreement with experiment to within 1 kcal/mol is not achieved even with the most elaborate multireference CI (configuration interaction) wave functions and largest basis sets currently feasible, it is possible to obtain agreement to within about 2 kcal/mol, or 1 percent of the dissociation energy. At this level it is necessary to account for core-valence correlation effects and to include up to h-type functions in the basis. The effect of i-type functions, the use of different reference configuration spaces, and basis set superposition error were also investigated. After discussing these results, the remaining sources of error in our best calculations are examined.

Almlof, Jan↗