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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 NTRS1973

Molecule formation by inverse predissociation

The general theory of inverse predissociation is described, and is applied to specific molecules. The list of molecules which can be formed by radiative association will be lengthened considerably by considering this phenomenon. Typical rate constants for diatoms will lie in the range 10 to the minus 16th power to 10 to the minus 20th power cu cm/sec/molecule, with the heavy atom molecules such as CN, CO, or NO generally having larger rates than the hydrides. An attempt is made to point out what molecular characteristics determine the radiative association rate and also to make estimates of what rates may be expected for various interstellar molecules. The formal theory is developed, and the molecular properties are discussed which determine the inverse predissociation rate. The details of the theory as applied to specific interstellar molecules are studied.

Julienne, P. S.↗
NASA NTRS1965

Theory of Intramolecular Relaxation Processes

A master equation is derived to describe internal relaxation processes in molecular systems with a relatively small number of degrees of freedom. It is an inhomogeneous equation, taking into account nondiagonal elements of the coarse‐grained density matrix which prove to be the most relevant ones for the problem under consideration. Various relaxational time scales, inherent in a molecular system, can thus be shown to exist. Relaxation mechanisms and equilibrium states on these time scales can be determined. The general character and different types of solutions of the master equation are investigated. The theory is applied to internal vibrational relaxation and intramolecular rearrangement (isomerization) reactions.

Hofacker, G. Ludwig↗
NASA NTRS1971

Irradiation of linear polyethylene - Partitioning between sol and gel.

Investigation of the importance of chain-scission processes and of the applicability of the general theory of network formation to polyethylene with respect to critical conditions for gelation, using molecular weight fractions of linear polyethylene irradiated at 133 C. The partitioning between sol and gel was found to adhere to the theory just beyond the gel point. Deviations from theory occurred as the irradiation dosage was increased. It was concluded that main-chain scission at the temperatures concerned is not a significant process.

Rijke, A. M.↗
NASA NTRS1983

A note on compressibility and energy cascade in turbulent molecular clouds

Observed velocity-size correlations are reexamined in the light of an improved theory of turbulent energy cascade that is developed. It is shown that observed velocity-size correlations cannot be compared with the Kolmogorov law, which is based on incompressible turbulent flow. The fact that the log v-log(l/rho) scaling law (v the turbulent velocity, l the associated region size, and rho the fluid density) predicted for compressible energy cascade is always steeper than that observed in molecular clouds indicates the injection rather than the dissipation of mechanical energy at smaller scales of motion. It is also shown that the concept of strict energy cascade may not be generally applicable in the interstellar medium. The agreement between theory and observation turns out to be best for small cool clouds and cloud cores, suggesting that, for these regions at least, the dominant process in establishing the observed v-l-rho correlation is a turbulent energy cascade.

Fleck, R. C., Jr.↗
NASA NTRS1993

Relativistic effects on the bonding and properties of the hydrides of platinum

The ground state of PtH2 and several low-lying states of PtH(+) and PtH have been studied at the all-electron self-consistent-field level of theory to examine the importance of relativistic effects. The results of calculations based on Dirac-Hartree-Fock theory, nonrelativistic theory, and the spin-free no-pair relativistic approximation of Hess are compared to separate the effects of the spin-free terms and the spin-orbit terms of the Hamiltonian on the relativistic corrections to the molecular properties. Comparison is also made between first-order perturbation theory including the one-electron spin-free terms and the method of Hess to determine the size of effects beyond first order. It is found that the spin-orbit interaction significantly affects the properties and energetics of these molecules because of the participation of the Pt 5d orbitals in the bonding, and that effects beyond first order in perturbation theory are large. Any treatment of Pt compounds will have to include both the spin-free and spin-orbit interactions for an accurate description.

Dyall, Kenneth G.↗
NASA NTRS2000

Protein Crystal Growth Dynamics and Impurity Incorporation

The general concepts and theories of crystal growth are proven to work for biomolecular crystallization. This allowed us to extract basic parameters controlling growth kinetics - free surface energy, alpha, and kinetic coefficient, beta, for steps. Surface energy per molecular site in thermal units, alpha(omega)(sup 2/3)/kT approx. = 1, is close to the one for inorganic crystals in solution (omega is the specific molecular volume, T is the temperature). Entropic restrictions on incorporation of biomolecules into the lattice reduce the incorporation rate, beta, by a factor of 10(exp 2) - 10(exp 3) relative to inorganic crystals. A dehydration barrier of approx. 18kcal/mol may explain approx. 10(exp -6) times difference between frequencies of adding a molecule to the lattice and Brownian attempts to do so. The latter was obtained from AFM measurements of step and kink growth rates on orthorhombic lysozyme. Protein and many inorganic crystals typically do not belong to the Kossel type, thus requiring a theory to account for inequivalent molecular positions within its unit cell. Orthorhombic lysozyme will serve as an example of how to develop such a theory. Factors deteriorating crystal quality - stress and strain, mosaicity, molecular disorder - will be reviewed with emphasis on impurities. Dimers in ferritin and lysozyme and acetylated lysozyme, are microheterogeneous i.e. nearly isomorphic impurities that are shown to be preferentially trapped by tetragonal lysozyme and ferritin crystals, respectively. The distribution coefficient, K defined as a ratio of the (impurity/protein) ratios in crystal and in solution is a measure of trapping. For acetylated lysoyzme, K = 2.15 or, 3.42 for differently acetylated forms, is independent of both the impurity and the crystallizing protein concentration. The reason is that impurity flux to the surface is constant while the growth rate rises with supersaturation. About 3 times lower dimer concentration in space grown ferritin and lysozyme crystals might be examples explaining higher quality of the space grown protein crystal. Depletion of solution with respect to isomorphic impurities around a growing crystal may be K times deeper than with respect to the crystallizing protein.

Chernov, Alex A.↗
NASA NTRS1995

The Submillimeter Wave Astronomy Satellite

The Submillimeter Wave Astronomy Satellite (SWAS) mission is dedicated to the study of star formation and interstellar chemistry. To carry out this mission, SWAS will survey dense (n(sub H2) greater than 10(exp 3) cm(exp -3)) molecular clouds within our galaxy in either the ground-state of a low-lying transition of five astrophysically important species: H2O, H2O-18, O2, CI, and CO-13. By observing these lines SWAS will: (1) test long-standing theories that predict that these species are the dominant coolants of molecular clouds during the early stages of their collapse to form stars and planets, and (2) supply heretofore missing information about the abundanceof key species central to the chemical models of dense interstellar gas. SWAS will employ two independent Schottky barrier diode mixers, passively cooled to approx. 150 K, coupled to a highly efficient 54 x 68 cm off-axis Cassegrain antenna. During its two year mission, SWAS will observe giant and dark cloud cores with the goal of detecting or setting an upper limit on the water abundance of 3 x 10(exp -6) and on th molecular oxygen abundances of 2 x 10(exp -6), both relative to H2. In addition, advantage will be taken of SWAS's relatively large beamsize of 3.2 x 4.0 arcminutes at 551 GHz and 3.6 x 4.5 arcminutes at 492 GHz to obtain large-area (approx. 1 deg x 1 deg) maps of giant and dark clouds in the CO-13 and CI lines. SWAS is scheduled for launch in mid-1995.

Melnick, Gary J.↗
NASA NTRS1976

Storage and recombination of atomic H in solid H2

A phenomenological rate process theory is developed for the storage and rapid recombination of atomic hydrogen free radicals in a crystalline molecular hydrogen solid at temperatures in the range of about 0.1-4 K. It is shown that such a theory can account quantitatively for the recently observed dependence of the storage time on the storage temperature, for the maximum concentration of trapped H atoms, and for the time duration of the energy release in the tritium decay experiments of Webeler. The theory predicts that maximum atomic hydrogen concentrations of the order 10 to the 20th per cu cm are realizable for storage temperatures in the vicinity of 0.14 K.

Rosen, G.↗
NASA NTRS1986

Molecular clouds and periodic events in the geologic past

The suggestion that a claimed 30 Myr period in the geologic past resulted from cometary impacts following encounters with molecular clouds as the solar system oscillates about the galactic plane poses a well-defined problem in the theory of shot noise. All recent CO surveys of the Galaxy clearly indicate that the concentration of molecular clouds in the galactic plane is not sufficient to allow a statistically significant period to be extracted from the small number of dated events. Of the order of 1000 events is probably required to obtain a credible period.

Thaddeus, P.↗
NASA NTRS1968

Kinetic theory of optical maser

Kinetic theory of interactions between coherent light waves and polarized molecular beams at near free molecular flow regions

Chiu, H. H.↗
NASA NTRS1983

Pressure dependence of intramolecular mode frequencies in solid N2, O2, and CO2

A microscopic description of the pressure dependence of intramolecular vibrational modes in simple molecular crystals has been formulated using a classical perturbation theory. Quantitative agreement with experiment is demonstrated and it is shown that frequency changes at phase transitions are large enough to be observed optically.

Etters, R. D.↗
NASA NTRS1978

Laser-enhanced dynamics in molecular rate processes

The present discussion deals with some theoretical aspects associated with the description of molecular rate processes in the presence of intense laser radiation, where the radiation actually interacts with the molecular dynamics. Whereas for weak and even moderately intense radiation, the absorption and stimulated emission of photons by a molecular system can be described by perturbative methods, for intense radiation, perturbation theory is usually not adequate. Limiting the analysis to the gas phase, an attempt is made to describe nonperturbative approaches applicable to the description of such processes (in the presence of intense laser radiation) as electronic energy transfer in molecular (in particular atom-atom) collisions; collision-induced ionization and emission; and unimolecular dissociation.

George, T. F.↗
NASA NTRSDate not supplied

Efficient Implementation for Unitary Coupled Cluster State Preparation for Near-Term Quantum Computers

Unitary coupled cluster theory (UCC) is a common wave function ansatz for quantum simulation of molecular electronic structure using the variational quantum eigenvalue solver (VQE). Even for small molecules using a double-ζ basis, the number of variational parameters required to minimize the electronic energy (i.e., optimize the circuit) is large and beyond the reach of current quantum computers. For example, a circuit simulating C2 using the UCCSD ansatz and the cc-pVDZ basis set with frozen-core will require over 10,000 variational parameters and a Hilbert space of over 10^8 determinants. To make progress on simulating such molecular systems on near-term quantum computers, we explore how much of the optimization can be approximately prepared with classical simulation while reducing the number of optimization steps performed on a quantum device. Recently, Chen, Cheng, and Freericks [J. Chem. Theory Comput. 2021, 17, 841-847] presented an algorithm for the factorized form of the UCC ansatz that allows for efficient UCC optimizations on classical hardware. We flip the algorithm around and use it to prepare approximate quantum circuits for systems that require a large number of qubits to represent. We will present results from our implementation and discuss strategies for incorporating this implementation for algorithms involving near-term quantum computers.

J Wayne Mullinax↗
NASA NTRSDate not supplied

Efficient Implementation for Unitary Coupled Cluster State Preparation for Near-Term Quantum Computers

Unitary coupled cluster theory (UCC) is a common wave function ansatz for quantum simulation of molecular electronic structure using the variational quantum eigenvalue solver (VQE). Even for small molecules using a double-ζ basis, the number of variational parameters required to minimize the electronic energy (i.e., optimize the circuit) is large and beyond the reach of current quantum computers. For example, a circuit simulating C2 using the UCCSD ansatz and the cc-pVDZ basis set with frozen-core will require over 10,000 variational parameters and a Hilbert space of over 10^(8) determinants. To make progress on simulating such molecular systems on near-term quantum computers, we explore how much of the optimization can be approximately prepared with classical simulation while reducing the number of optimization steps performed on a quantum device. Recently, Chen, Cheng, and Freericks [J. Chem. Theory Comput. 2021, 17, 841-847] presented an algorithm for the factorized form of the UCC ansatz that allows for efficient UCC optimizations on classical hardware. We flip the algorithm around and use it to prepare approximate quantum circuits for systems that require a large number of qubits to represent. We will present results from our implementation and discuss strategies for incorporating this implementation for algorithms involving near-term quantum computers.

Quantum Computing↗
NASA NTRSDate not supplied

Efficient Implementation for Unitary Coupled Cluster State Preparation for Near-Term Quantum Computers

Unitary coupled cluster theory (UCC) is a common wave function ansatz for quantum simulation of molecular electronic structure using the variational quantum eigenvalue solver (VQE). Even for small molecules using a double-ζ basis, the number of variational parameters required to minimize the electronic energy (i.e., optimize the circuit) is large and beyond the reach of current quantum computers. For example, a circuit simulating C2 using the UCCSD ansatz and the cc-pVDZ basis set with frozen-core will require over 10,000 variational parameters and a Hilbert space of over 10^(8) determinants. To make progress on simulating such molecular systems on near-term quantum computers, we explore how much of the optimization can be approximately prepared with classical simulation while reducing the number of optimization steps performed on a quantum device. Recently, Chen, Cheng, and Freericks [J. Chem. Theory Comput. 2021, 17, 841-847] presented an algorithm for the factorized form of the UCC ansatz that allows for efficient UCC optimizations on classical hardware. We flip the algorithm around and use it to prepare approximate quantum circuits for systems that require a large number of qubits to represent. We will present results from our implementation and discuss strategies for incorporating this implementation for algorithms involving near-term quantum computers.

Quantum Computing↗
NASA NTRS1972

Electrical conductivity of condensed molecular hydrogen in the giant planets

Theoretical interpretation of several phenomena concerning Jupiter and Saturn depends upon the electrical conductivity of molecular hydrogen which, according to present models, forms the outermost layer of both planets. The layer starts at the transition pressure between the metallic and the molecular form of hydrogen, that is around 1 Mbar, and extends to the outside limits of the atmosphere. Whether at the highest pressures (and temperatures) this layer is a solid or a dense fluid is not certain. In any case, the fluid is in supercritical condition so that there is only a gradual transition from dense liquid to a gaseous form. The two theories which require specific values of the conductivity of the condensed molecular hydrogen are those pertaining to the generation of a magnetic field in the liquid hydrogen rather than in the deep metallic interior (HIDE, 1967), and those concerned with the electromagnetic coupling and exchange of angular momentum between the liquid core and the solid molecular hydrogen mantle.

Smoluchowski, R.↗