Search NASA⌕ Search

SEARCH · Search NASA

Results for “MOLECULAR THEORY”

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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

Determining the Molecular Growth Mechanisms of Tetragonal Lysozyme Crystals

Studies of the growth of tetragonal lysozyme crystals employing atomic force microscopy (AFM) have shown the advantages of this technique in investigating the growth mechanisms of protein crystals [1]. The resolution of these studies was in the micron range, which revealed surface features such as the occurrence of dislocations and 2D nucleation islands, similar to those found in inorganic systems. They clearly showed that the crystals grew by these surface growth mechanisms. However, the studies also revealed some surprising features, such as bimolecular growth step heights and pronounced growth anisotropies on the (110) face, which could not be explained. In previous studies we employed Periodic Bond Chain (PBC) theory to tetragonal lysozyme crystal growth and found that the crystals were constructed by strongly bonded molecular chains forming helices about the 43 axes [2,3]. The helices were connected to each other with weaker bonds. The growth process was shown to proceed by the formation of these 43 helices, resulting in bimolecular growth steps on the (110) face. It was also shown to explain many other observations on tetragonal lysozyme crystal growth. Although PBC analysis is not a new technique [4], it has not been widely used as the mechanisms predicted from it could not be experimentally verified. In this study the growth process of these crystals was investigated, particularly for the (110) face, employing some newly developed high resolution AFM techniques. These techniques allowed individual lysozyme molecules on the crystal faces to be resolved and predictions from PBC analyses to be tested. The analyses had shown that of the two possible packing arrangements on (110) faces, only one would actually occur. Employing the first of the newly developed techniques, these faces were scanned by high resolution AFM. The resulting images were then compared with the theoretically constructed images for the two possible packing arrangements on the (110) face. The theoretical images were constructed by convolution of the crystal surface shape obtained from crystallographic data with the AFM tip shape. The comparison confirmed the prediction that the molecular packing arrangement of these faces corresponded to that for complete 43 helices. The second AFM technique that was developed was used to follow the growth process by measuring the dimensions of individual growth units on the (110) face. Linescans across a growth step, performed near the saturation limit of the crystals, allowed the growth unit dimensions to be measured. These measurements showed that growth on the (110) face proceeded by the formation of new 43 helices from the addition of at least tetramer units in the [110] direction. In the [001] direction growth proceeded by the addition of various aggregate units corresponding to the 4(sub 3) helices.

Li, Huayu↗
NASA NTRS1987

Structure and kinematics of the molecular spiral arms in M51

Mapping of the CO(1-0) emission from the spiral galaxy was made with the Onsala 20 m antenna. The observations show that the emission is considerably enhanced in spiral arms which appear to originate as intense ridges of emission about 1 kpc from the nucleus. One of the main objectives for the 1986 observations was to study the variations of the tangential velocity component of molecular gas across a spiral arm. The radial velocity was found to have a velocity shift similar to that predicted by the density wave theory. The present (1986) observations of the inner southern spiral arm of M51 show that the tangential velocity component also behaves in a way which conforms with the density wave model. The molecular arms were compared with the H alpha ionized gas arms of Tully (1974) and it was found that the ionized gas appears to have its maximum intensity slightly outside the molecular arm.

Rydbeck, G.↗
NASA NTRS1994

General analytic results for nonlinear waves and solitons in molecular clouds

We study nonlinear wave phenomena in self-gravitating fluid systems, with a particular emphasis on applications to molecular clouds. This paper presents analytical results for one spatial dimension. We show that a large class of physical systems can be described by theories with a 'charge density' q(rho); this quantity replaces the density on the right-hand side of the Poisson equation for the gravitational potential. We use this formulation to prove general results about nonlinear wave motions in self-gravitating systems. We show that in order for stationary waves to exist, the total charge (the integral of the charge density over the wave profile) must vanish. This 'no-charge' property for solitary waves is related to the capability of a system to be stable to gravitational perturbations for arbitrarily long wavelengths. We find necessary and sufficient conditions on the charge density for the existence of solitary waves and stationary waves. We study nonlinear wave motions for Jeans-type theories (where q(rho) = rho-rho(sub 0)) and find that nonlinear waves of large amplitude are confined to a rather narrow range of wavelengths. We also study wave motions for molecular clouds threaded by magnetic fields and show how the allowed range of wavelengths is affected by the field strength. Since the gravitational force in one spatial dimension does not fall off with distance, we consider two classes of models with more realistic gravity: Yukawa potentials and a pseudo two-dimensional treatment. We study the allowed types of wave behavior for these models. Finally, we discuss the implications of this work for molecular cloud structure. We argue that molecular clouds can support a wide variety of wave motions and suggest that stationary waves (such as those considered in this paper) may have already been observed.

Adams, Fred C.↗
NASA NTRS1979

Atomic to molecular hydrogen transition in interstellar clouds

The photodestruction of molecular hydrogen is reexamined in the context of recent observational data. Improvements in the theory of radiation transfer are made by using a more accurate self-shielding integral, treating anisotropic scattering by dust grains, and including photodissociation from excited rotational states. The total column density of hydrogen required to obtain 10% conversion decreases with a parameter, epsilon, the ratio of the formation rate to the destruction rate, as epsilon to the -m power, with m in the range 1.4-1.6. Satisfactory agreement with the data for thicker diffuse clouds is obtained for epsilon of about 0.00006.

Federman, S. R.↗
NASA NTRS1978

Molecular rotation and reorientation - Microscopic and hydrodynamic contributions

The relative roles of microscopic and hydrodynamic contributions to molecular rotation and reorientation are examined within the framework of the microscopic boundary layer theory recently proposed by the authors. The theory is applied to rough spheres, for which computer simulation data are available and to experimental results on spherical top molecules. Attention is focused on rotational diffusion constants, the kappa parameter introduced by Kivelson et al., and orientational relaxation times. It is shown that, while collective effects are present and often nonnegligible, the motion of small molecules is dominated by its microscopic aspects. Experimental trends which can incorrectly suggest dominance by hydrodynamic contributions are discussed in some detail. Finally, the transition to the regime where collective effects are dominant is considered.

Hynes, J. T.↗
NASA NTRS1994

Predicting radiative heat transfer in thermochemical nonequilibrium flow fields. Theory and user's manual for the LORAN code

The theory for radiation emission, absorption, and transfer in a thermochemical nonequilibrium flow is presented. The expressions developed reduce correctly to the limit at equilibrium. To implement the theory in a practical computer code, some approximations are used, particularly the smearing of molecular radiation. Details of these approximations are presented and helpful information is included concerning the use of the computer code. This user's manual should benefit both occasional users of the Langley Optimized Radiative Nonequilibrium (LORAN) code and those who wish to use it to experiment with improved models or properties.

Chambers, Lin Hartung↗
NASA NTRS1999

Direct Detection Doppler Lidar for Spaceborne Wind Measurement

The theory of double edge lidar techniques for measuring the atmospheric wind using aerosol and molecular backscatter is described. Two high spectral resolution filters with opposite slopes are located about the laser frequency for the aerosol based measurement or in the wings of the Rayleigh - Brillouin profile for the molecular measurement. This doubles the signal change per unit Doppler shift and improves the measurement accuracy by nearly a factor of 2 relative to the single edge technique. For the aerosol based measurement, the use of two high resolution edge filters reduces the effects of background, Rayleigh scattering, by as much as an order of magnitude and substantially improves the measurement accuracy. Also, we describe a method that allows the Rayleigh and aerosol components of the signal to be independently determined. A measurement accuracy of 1.2 m/s can be obtained for a signal level of 1000 detected photons which corresponds to signal levels in the boundary layer. For the molecular based measurement, we describe the use of a crossover region where the sensitivity of a molecular and aerosol-based measurement are equal. This desensitizes the molecular measurement to the effects of aerosol scattering and greatly simplifies the measurement. Simulations using a conical scanning spaceborne lidar at 355 nm give an accuracy of 2-3 m/s for altitudes of 2-15 km for a 1 km vertical resolution, a satellite altitude of 400 km, and a 200 km x 200 km spatial.

Korb, C. Laurence↗
NASA NTRS1994

Achieving Chemical Accuracy with Coupled-Cluster Theory

Due to formal and computational advances in coupled-cluster theory over the past few years, it is now possible to obtain very accurate molecular geometries, vibrational frequencies, heats of formation, binding energies, and vertical electronic excitation energies. The present monograph reviews the advances that have lead to the current state-of-the art, and also summarizes selected examples from the published literature.

Lee, Timothy J.↗
NASA NTRS1995

Vibrational and Electronic Energy Transfer and Dissociation of Diatomic Molecules by Electron Collisions

At high altitudes and velocities equal to or greater than the geosynchronous return velocity (10 kilometers per second), the shock layer of a hypersonic flight will be in thermochemical nonequilibrium and partially ionized. The amount of ionization is determined by the velocity. For a trans atmospheric flight of 10 kilometers per second and at an altitude of 80 kilometers, a maximum of 1% ionization is expected. At a velocity of 12 - 17 kilometer per second, such as a Mars return mission, up to 30% of the atoms and molecules in the flow field will be ionized. Under those circumstances, electrons play an important role in determining the internal states of atoms and molecules in the flow field and hence the amount of radiative heat load and the distance it takes for the flow field to re-establish equilibrium. Electron collisions provide an effective means of transferring energy even when the electron number density is as low as 1%. Because the mass of an electron is 12,760 times smaller than the reduced mass of N2, its average speed, and hence its average collision frequency, is more than 100 times larger. Even in the slightly ionized regime with only 1% electrons, the frequency of electron-molecule collisions is equal to or larger than that of molecule-molecule collisions, an important consideration in the low density part of the atmosphere. Three electron-molecule collision processes relevant to hypersonic flows will be considered: (1) vibrational excitation/de-excitation of a diatomic molecule by electron impact, (2) electronic excitation/de-excitation, and (3) dissociative recombination in electron-diatomic ion collisions. A review of available data, both theory and experiment, will be given. Particular attention will be paid to tailoring the molecular physics to the condition of hypersonic flows. For example, the high rotational temperatures in a hypersonic flow field means that most experimental data carried out under room temperatures are not applicable. Also, the average electron temperature is expected to be between 10,000 and 20,000 K. Thus only data for low energy electrons are relevant to the model.

Huo, Winifred M.↗
NASA NTRS1994

New calculations on the ion-molecule processes C2H2(+) + H2 --> C2H3(+) + H and C2H2(+) + H2 --> C2H4+

New high-level quantum chemical calculations have been undertaken to understand the rates and mechanisms of the reactive and associative channels for the reactants C2H2(+) + H2. The reactive channel, which produces C2H3(+) + H, has been shown to be slightly endothermic, confirming earlier calculations at a somewhat lower level and in agreement with some recent experimental work. The associative channel, leading to C2H4+, has been shown to proceed via a transition state with negative energy relative to the reactants, so that association is predicted to be efficient. This result is in conflict with an earlier theoretical study but in agreement with low-temperature experimental measurements.

NASA Discipline Exobiology↗
NASA NTRSDate not supplied

Metal Hydroxide and Oxyhydroxide Gas Database

In a high temperature combustion situation such as a gas turbine or rocket engine, combustion products include water vapor. This water vapor reacts with oxides in the hot-gas-path to form volatile hydroxides and oxyhydroxides. The oxides may be structural oxide components or protective oxides on alloys or non-oxide ceramics. In either case, this enhanced volatilization leads to degradation of components. Reliable thermochemical data for many metal hydroxides and oxyhydroxides has not been available. We review a database put together at NASA over many years based on experimental and ab initio computations for thermochemical data of Al, Si, Ti, Cr, Mn, Y, Zr, La, Ta, Gd, and Yb hydroxides and oxyhydroxides. Experimental methods for measuring thermodynamic quantities of metal hydroxides and oxyhydroxides are limited since the required high temperatures and high pressures preclude many conventional methods. Nonetheless, transpiration has proven a valuable tool in our laboratories for the Si-O-H, Cr-O-H, and Ti-O-H systems. Data are analyzed with second and third law methods. These data can be leveraged with quantum chemistry to provide reliable free energy functions for the third law calculation and comparison to the derived enthalpies of formation. Both wave function and DFT methods can be utilized for deriving the thermodynamic functions for the various metal hydroxides and oxyhydroxides. We have found that, in general, reasonable molecular geometries and spectroscopic data can be derived with a relatively low level of theory, i.e. DFT with the B3LYP functional. Accurate calculations of the enthalpy of formation require higher levels of theory, such as the Coupled Cluster, Singles, Doubles, and perturbative Triples CCSD(T) approach with complete basis sets (CBS). Also, corrections for hindered rotations and anharmonicity are necessary. For some symmetries, the anharmonic correction has proven to be a challenge and we have found that this is only treated properly by certain codes. The database lists the fHo(298), So(298), and Cp in the form Cp = A + BT + CT2 + D/T + E/T2, where A, B, C, D, and E are the fitting constants. Thus, it can be easily used in any of the common computational thermochemistry codes. To date, the database contains 51 gaseous species of the formula MOx(OH)y.

Metal Hydroxides↗
NASA NTRS1991

Optical properties of grains in molecular clouds and accretion disks

A baseline model of the composition and abundances of grains and gases in molecular cloud cores and accretion disks around young stars is defined by employing: a wide range of astronomical data and theory; the composition of primitive bodies in the solar system; and solar elemental abundances. It is proposed that in the coldest portions of these objects the major grain species include amorphous olivine, amorphous orthopyroxene, volatile and refractory organics, water ice, troilite, and metallic iron. Using a combination of laboratory measurements of optical constants and asymptotic theory, values of the real and imaginary indices of refraction of these grain species over a wavelength range that runs from the vacuum UV to the radio domain are derived. Auxiliary information for these grain species, such as their vaporization temperatures bulk densities, and their fractional abundances by mass. The above information on grain properties in molecular cloud cores and accretion disks is used to estimate the Rosseland mean opacity of the grains in both environments and the IR and microwave opacity of grains in accretion disks.

Pollack, J. B.↗
NASA NTRS1991

Spray measurements of aerothermodynamic effect on disintegrating liquid jets

An experimental investigation was made to determine the effect of atomizing gas mass flux and temperature on liquid jet breakup in sonic velocity gas flow. Characteristic drop size data were obtained by using the following atomizing gases: nitrogen, argon, and helium to breakup water jets in high velocity gas flow. A scattered light scanning instrument developed at Lewis Research Center was used to measure Sauter mean diameter (SMD). The three gases gave a molecular weight range of 4 to 40 and atomizing gas mass flux and temperature were varied from 6 to 50 g/sq cm and 275-400 K, respectively. The ratio of liquid jet diameter to SMD, D(sub 0)/D(sub 32), was correlated with aerodynamic and liquid-surface force ratios, i.e., the product of the Weber and Reynolds number, We Re, the gas to liquid density ratio, rho(sub g)/rho(sub 1) g and also the molecular scale dimensionless group, rho(sub 1)(Vm exp 3)/ mu(sub 1) g, to give the following expression: D(sub 0)/D(sub 32) = 0.90 x 10(exp -8) x (We Re rho sub g/rho sub 1)exp 0.44 x (rho sub 1 Vm exp 3/mu sub 1 g)exp 0.67 where We Re = ((rho sub g)exp 2(D sub 0)exp 2(V sub C)exp3))/ mu sub 1 sigma, mu sub 1 is liquid viscosity, sigma is surface tension, V sub C is the acoustic gas velocity, V sub m is the RMS velocity of gas molecules, and g is the acceleration of gas molecules due to gravity. Good agreement was obtained with atomization theory for liquid-jet breakup in the regime of aerodynamic stripping. Also, due to its low molecular weight and high acoustic velocity, helium was considerably more effective than nitrogen or argon in producing small-droplet sprays with values of D(sub 32) on the order of 5 microns.

Ingebo, Robert D.↗
NASA NTRS1977

Photoabsorption in formaldehyde

Theoretical studies of the vertical electronic dipole excitation and ionization spectra in molecular formaldehyde are reported. The investigations relied on configuration-interaction calculations and moment-theory techniques. A double-zeta basis of contracted Gaussian-lobe functions supplemented with appropriate polarization and bond functions was used to construct Fock spectra in C(2 nu) symmetry for certain states near the ground state equilibrium geometry. The ionization energies, discrete vertical transition frequencies, and oscillator strengths for occupied and vertical Fock orbitals are in general accord with experimental determinations and other theoretical calculations. Stieltjes and Chebyshev vertical electronic photoionization profiles were calculated and found to be in good agreement with appropriately averaged photoionization-mass spectrometric measurements of the cross section for parent H2CO(+) ion production.

Langhoff, P. W.↗
NASA NTRS2002

Collaborative Simulation Grid: Multiscale Quantum-Mechanical/Classical Atomistic Simulations on Distributed PC Clusters in the US and Japan

A multidisciplinary, collaborative simulation has been performed on a Grid of geographically distributed PC clusters. The multiscale simulation approach seamlessly combines i) atomistic simulation backed on the molecular dynamics (MD) method and ii) quantum mechanical (QM) calculation based on the density functional theory (DFT), so that accurate but less scalable computations are performed only where they are needed. The multiscale MD/QM simulation code has been Grid-enabled using i) a modular, additive hybridization scheme, ii) multiple QM clustering, and iii) computation/communication overlapping. The Gridified MD/QM simulation code has been used to study environmental effects of water molecules on fracture in silicon. A preliminary run of the code has achieved a parallel efficiency of 94% on 25 PCs distributed over 3 PC clusters in the US and Japan, and a larger test involving 154 processors on 5 distributed PC clusters is in progress.

Kikuchi, Hideaki↗
NASA NTRS1985

Molecular orbital predictions of the vibrational frequencies of some molecular ions

The initial detections of IR vibration-rotation bands in polyatomic molecular ions by recent spectroscopic advances were guided by ab initio prediction of vibrational frequencies. The present calculations predict the vibrational frequencies of additional ions which are candidates for laboratory analysis. Neutral molecule vibrational frequencies were computed at three levels of theory and then compared with experimental data; the effect of scaling was also investigated, in order to determine how accurately vibrational frequencies could be predicted. For 92 percent of the frequencies examined, the relatively simple HF/6-31G theory's vibrational frequencies were within 100/cm of experimental values, with a mean absolute error of 49/cm. On this basis, the frequencies of 30 molecular ions (many possessing astrophysical significance) were computed.

Defrees, D. J.↗