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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 127 records · Page 7
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NASA NTRSDate not supplied

Discrete Rotational Energy for Polyatomic Molecules in Direct Simulation Monte Carlo

The environments experienced by vehicles upon entry into planetary atmospheres generally result in severe aerothermodynamic loading. These flows are characterized by the formation of strong shock waves, behind which high temperatures and non-equilibrium environments are generated, and the accurate prediction of internal energy relaxation and chemical kinetics becomes important. This manuscript focuses on the internal relaxation of the rotational energy of polyatomic molecules. Previous work has described the implementation of a discrete rotational energy model for diatomic molecules (linear rotators). Later, Gimelshein et. al extended this model to include polyatomic molecular internal energies. However, they did not include details on how to generate the particles at equilibrium conditions and centrifugal distortion was not included in their model. The purpose of the present study is to extend the afore-mentioned models to the treatment of discrete rotational energy in polyatomic molecules with the addition of centrifugal distortion. An overview of the background theory needed for the implementation of the model will be given followed by the model itself and verification of the model. For example, sampled versus Boltzmann distributions are compared in Figure 1 for CH3 (oblate rotator – two quantum numbers) and examples of thermal relaxation behavior for linear and non-linear rotators are presented in Figure 2. In addition, comparisons of thermophysical properties will be presented, as well as examples of adiabatic relaxation and application to hypersonic flow.

Rarefied Gas Dynamics↗
NASA NTRS1990

Central-force potentials for interaction of rotationally and vibrationally excited molecules

A general and computationally efficient approach evaluating the central-force potentials for interaction of rotationally and vibrationally excited molecules and molecular ions is presented. Examples of numerical calculations are given for interactions of diatomic systems (H2, N2 and O2) in ground electronic states. The approach can be applied in a straightforward way to interactions of atoms and atomic ions with diatomic molecules in arbitrary rotational-vibrational states.

Kunc, Joseph A.↗
NASA NTRS1981

Radio observations of molecules in the interstellar gas

Since 1968, radio astronomy has made it possible to identify nearly 50 molecules in the dense concentrations of the interstellar gas now generally termed molecular clouds. Most interstellar molecules are familiar stable compounds. However, one-fifth of the discovered species are ions, radicals, and acetylenic carbon chains so reactive in the laboratory that before being detected in space they had rarely been observed or were entirely unknown. The heavy atom backbone of the known interstellar molecules is a linear chain of C, N, O, or S. Si is found in two diatomic molecules. Rings and branched chains are missing. The most readily observed spectral lines of most interstellar molecules correspond to rotational transitions at millimeter wavelengths. These are generally excited by H2 collisions. A number of rare isotopic species are observed in interstellar molecules. Isotopic ratios differing from those on Earth exist, and can in almost all cases be attributed to stellar nucleosynthesis since the formation of the solar system.

Thaddeus, P.↗
NASA NTRS1991

Molecules and chains in a strong magnetic field - Statistical treatment

A Thomas-Fermi-Dirac-Weizsaecker statistical model is developed and employed to investigate diatomic molecules and infinite molecular chains in strong magnetic fields. The standard magnetic Thomas-Fermi-Dirac kinetic, potential, and exchange energy functionals are supplemented by a gradient correction to the kinetic energy. The numerical method used for solving this system in two spatial dimensions is detailed. Numerical solutions for a wide range of magnetic strengths and elements are presented to demonstrate the robustness, as well as the limitations, of the statistical approach. These calculations qualitatively reproduce many of the results of detailed quantum mechanical treatments. For example, the fractional binding energy is greatest for low atomic numbers and for strong magnetic fields.

Abrahams, Andrew M.↗
NASA NTRS1974

Multiconfiguration self-consistent-field calculation of the dipole moment function of CO/X 1 sigma +/

Using the optimized valence configurations (OVC) multiconfiguration self-consistent-field (MCSCF) method, the dipole moment function for the ground state of CO in the vicinity of the equilibrium internuclear distance has been calculated. The OVC MCSCF calculation results are compared with existing Hartree-Fock and configuration interaction treatments of this molecule at single points and also the dipole moment function deduced from experimental infrared intensities. A general prescription for constructing OVC wavefunctions for diatomic molecules is also presented.

Billingsley, F. P., II↗
NASA NTRS1978

The coupled states approximation for scattering of two diatoms

The paper presents a detailed development of the coupled-states approximation for the general case of two colliding diatomic molecules. The high-energy limit of the exact Lippman-Schwinger equation is applied, and the analysis follows the Shimoni and Kouri (1977) treatment of atom-diatom collisions where the coupled rotor angular momentum and projection replace the single diatom angular momentum and projection. Parallels to the expression for the differential scattering amplitude, the opacity function, and the nondiagonality of the T matrix are reported. Symmetrized expressions and symmetrized coupled equations are derived. The present correctly labeled coupled-states theory is tested by comparing its calculated results with other computed results for three cases: H2-H2 collisions, ortho-para H2-H2 scattering, and H2-HCl.

Heil, T. G.↗
NASA NTRS1976

Rigid rotators

The two-particle, steady-state Schroedinger equation is transformed to center of mass and internuclear distance vector coordinates, leading to the free particle wave equation for the kinetic energy motion of the molecule and a decoupled wave equation for a single particle of reduced mass moving in a spherical potential field. The latter describes the vibrational and rotational energy modes of the diatomic molecule. For fixed internuclear distance, this becomes the equation of rigid rotator motion. The classical partition function for the rotator is derived and compared with the quantum expression. Molecular symmetry effects are developed from the generalized Pauli principle that the steady-state wave function of any system of fundamental particles must be antisymmetric. Nuclear spin and spin quantum functions are introduced and ortho- and para-states of rotators, along with their degeneracies, are defined. Effects of nuclear spin on entropy are deduced. Next, rigid polyatomic rotators are considered and the partition function for this case is derived. The patterns of rotational energy levels for nonlinear molecules are discussed for the spherical symmetric top, for the prolate symmetric top, for the oblate symmetric top, and for the asymmetric top. Finally, the equilibrium energy and specific heat of rigid rotators are derived.

Source record↗
NASA NTRS2019

Laser Rayleigh Scattering for Flow Density and Condensation Measurements in the Supercooled Mach-14 Free-Stream at AEDC Wind Tunnel No. 9

Laser Rayleigh scattering was used to investigate clusters in the free-stream flow at Arnold Engineering Development Center’s Tunnel 9 (T9). The facility was run at Mach-14, with a pure-N2 flow medium, and at several total pressures and temperatures. Using an excimer laser operating at 248 nm, the Rayleigh instrument imaged scattering from the focused laser beam in the free-stream. As a wind-tunnel flow is accelerated, it cools and approaches the condensation boundary. As a precursor to condensation, small clusters of molecules are first formed, but the individual clusters are too small to be spatially resolved in typical images of the beam. Thus clusters effectively add a spatially smooth background signal to the pure diatomic-molecule Rayleigh signal. The main result of the present work is that clustering was not significant. After correcting for interference by small particles imbedded in the T9 flow, cluster scattering was unobservable or smaller than one standard deviation (1-sigma) of the uncertainties for almost all tunnel runs. The total light scattering level was measured to be 1.05 +/- 0.15 (1-sigma) of the expected diatomic scattering, when averaged over the entire usable data set. This result included flow conditions that were supercooled to temperatures of ~ 20 K, about 25 K below the condensation limit of ~ 45 K. Thus the Mach-14 nozzle flow is essentially cluster-free for many supercooled conditions that might be used to extend the facility operating range to larger Reynolds numbers.

Herring, Gregory C.↗
NASA NTRS1973

Dissociative recombination of CH+ ions.

In recent studies of the formation of molecules in interstellar clouds, Solomon and Klemperer (1972) and Frisch (1972) were able to fit the observed ratios of CH+ and CH densities only with the assumption that the rate of dissociative recombination is extremely small. It is known that the rate for most diatomic molecules is relatively large, with the exception of H2+ and He2+ for which it is anomalously small. The present work explores the possibility that CH+ also has a low recombination rate. However, preliminary calculations yield a large rate of the dissociative recombination process, seemingly necessitating considerable revision of some recent models of interstellar clouds.

Bardsley, J. N.↗
NASA NTRS1984

Kinematics of the CS method for the treatment of molecular collisions

The problem of the quantum treatment of nonreactive collisions of two simple molecules or of an atom and a molecule is considered mathematically. Kinematical structure theorems analogous to the Wigner-Eckart theorem for scalar operators are derived for the transition operator (T-operator) of a two-molecule system, where, in addition to the usual conservation laws, certain additional conservation laws are presumed satisfied in a collision. The additional conservation laws were examined in order to develop a testable approximation scheme (CS method) for the specification of the kinematics of a system of two rigid diatomic molecules. The rand p-helicity basis states for a two-rigid rotor system are defined and unitary transformations established between these and conventional bases. It is found that only questionable criteria exist for testing the on-the-energy-shell matrix of a T(energy) operator for the presence of properties of two of the additional conservation laws.

Hahne, G. E.↗
NASA NTRS2004

Chemistry Modeling for Aerothermodynamics and TPS

Recent advances in supercomputers and highly scalable quantum chemistry software render computational chemistry methods a viable means of providing chemistry data for aerothermal analysis at a specific level of confidence. Four examples of first principles quantum chemistry calculations will be presented. The study of the highly nonequilibrium rotational distribution of nitrogen molecule from the exchange reaction N + N2 illustrates how chemical reactions can influence the rotational distribution. The reaction C2H + H2 is one example of a radical reaction that occurs during hypersonic entry into a methane containing atmosphere. A study of the etching of Si surface illustrates our approach to surface reactions. A recently developed web accessible database and software tool (DDD) that provides the radiation profile of diatomic molecules is also described.

Wang, Dun-You↗
NASA NTRS2005

Chemistry Modeling for Aerothermodynamics and TPS

Recent advances in supercomputers and highly scalable quantum chemistry software render computational chemistry methods a viable means of providing chemistry data for aerothermal analysis at a specific level of confidence. Four examples of first principles quantum chemistry calculations will be presented. Study of the highly nonequilibrium rotational distribution of a nitrogen molecule from the exchange reaction N + N2 illustrates how chemical reactions can influence rotational distribution. The reaction C2H + H2 is one example of a radical reaction that occurs during hypersonic entry into an atmosphere containing methane. A study of the etching of a Si surface illustrates our approach to surface reactions. A recently developed web accessible database and software tool (DDD) that provides the radiation profile of diatomic molecules is also described.

Wang, Dunyou↗
NASA NTRS1990

Theoretical investigation of gas-surface interactions

A Dirac-Hartree-Fock code was developed for polyatomic molecules. The program uses integrals over symmetry-adapted real spherical harmonic Gaussian basis functions generated by a modification of the MOLECULE integrals program. A single Gaussian function is used for the nuclear charge distribution, to ensure proper boundary conditions at the nuclei. The Gaussian primitive functions are chosen to satisfy the kinetic balance condition. However, contracted functions which do not necessarily satisfy this condition may be used. The Fock matrix is constructed in the scalar basis and transformed to a jj-coupled 2-spinor basis before diagonalization. The program was tested against numerical results for atoms with a Gaussian nucleus and diatomic molecules with point nuclei. The energies converge on the numerical values as the basis set size is increased. Full use of molecular symmetry (restricted to D sub 2h and subgroups) is yet to be implemented.

Dyall, Kenneth G.↗
NASA NTRS1984

Theoretical research program to predict the properties of molecules and clusters containing transition metal atoms

The primary focus of this research has been the theoretical study of transition metal (TM) chemistry. A major goal of this work is to provide reliable information about the interaction of H atoms with iron metal. This information is needed to understand the effect of H atoms on the processes of embrittlement and crack propagation in iron. The method in the iron hydrogen studies is the cluster method in which the bulk metal is modelled by a finite number of iron atoms. There are several difficulties in the application of this approach to the hydrogen iron system. First the nature of TM-TM and TM-H bonding for even diatomic molecules was not well understood when these studies were started. Secondly relatively large iron clusters are needed to provide reasonable results.

Walch, S.↗
NASA NTRS1971

Vibrational population distributions in nonequilibrium nozzle expansion flows

Experimental measurements and theoretical calculations of the vibrational population distribution in nonequilibrium nozzle expansion flows of gas mixtures are reported. These studies were directed toward determining whether vibrational energy exchange pumping could lead to laser action on the vibrational bands of a diatomic molecule. Three different types of experiments were conducted. These showed (1) that vibrational energy was preferentially transferred from N2 to CO in supersonic nozzle flows containing these gases; (2) that under some conditions this vibrational energy exchange pumping mechanism created population inversions in the vibrational levels of CO; and (3) that at large expansion ratios the magnitude of these population inversions was sufficient to sustain lasing in the nozzle. A theoretical model was developed to calculate vibrational state population distributions in gas dynamic expansions of a mixture of diatomic gases. Although only isothermal calculations have been completed, these data indicate that population inversions are predicted for conditions similar to those obtained in the nozzle expansion flows.

Watt, W. S.↗
NASA NTRS1991

Theoretical molecular studies of astrophysical interest

When work under this grant began in 1974 there was a great need for state-to-state collisional excitation rates for interstellar molecules observed by radio astronomers. These were required to interpret observed line intensities in terms of local temperatures and densities, but, owing to lack of experimental or theoretical values, estimates then being used for this purpose ranged over several orders of magnitude. A problem of particular interest was collisional excitation of formaldehyde; Townes and Cheung had suggested that the relative size of different state-to-state rates (propensity rules) was responsible for the anomalous absorption observed for this species. We believed that numerical molecular scattering techniques (in particular the close coupling or coupled channel method) could be used to obtain accurate results, and that these would be computationally feasible since only a few molecular rotational levels are populated at the low temperatures thought to prevail in the observed regions. Such calculations also require detailed knowledge of the intermolecular forces, but we thought that those could also be obtained with sufficient accuracy by theoretical (quantum chemical) techniques. Others, notably Roy Gordon at Harvard, had made progress in solving the molecular scattering equations, generally using semi-empirical intermolecular potentials. Work done under this grant generalized Gordon's scattering code, and introduced the use of theoretical interaction potentials obtained by solving the molecular Schroedinger equation. Earlier work had considered only the excitation of a diatomic molecule by collisions with an atom, and we extended the formalism to include excitation of more general molecular rotors (e.g., H2CO, NH2, and H2O) and also collisions of two rotors (e.g., H2-H2).

Flynn, George↗