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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

A priori predictions of the rotational constants for HC13N, HC15N, C5O

Ab initio molecular orbital theory is used to estimate the rotational constant for several carbon-chain molecules that are candidates for discovery in interstellar space. These estimated rotational constants can be used in laboratory or astronomical searches for the molecules. The rotational constant for HC13N is estimated to be 0.1073 +/- 0.0002 GHz and its dipole moment 5.4 D. The rotational constant for HC15N is estimated to be 0.0724 GHz, with a somewhat larger uncertainty. The rotational constant of C5O is estimated to be 1.360 +/- 2% GHz and its dipole moment 4.4. D.

NASA Discipline Exobiology↗
NASA NTRS2001

Membrane rejection of nitrogen compounds

Rejection characteristics of nitrogen compounds were examined for reverse osmosis, nanofiltration, and low-pressure reverse osmosis membranes. The rejection of nitrogen compounds is explained by integrating experimental results with calculations using the extended Nernst-Planck model coupled with a steric hindrance model. The molecular weight and chemical structure of nitrogen compounds appear to be less important in determining rejection than electrostatic properties. The rejection is greatest when the Donnan potential exceeds 0.05 V or when the ratio of the solute radius to the pore radius is greater than 0.8. The transport of solute in the pore is dominated by diffusion, although convective transport is significant for organic nitrogen compounds. Electromigration contributes negligibly to the overall solute transport in the membrane. Urea, a small organic compound, has lower rejection than ionic compounds such as ammonium, nitrate, and nitrite, indicating the critical role of electrostatic interaction in rejection. This suggests that better treatment efficiency for organic nitrogen compounds can be obtained after ammonification of urea.

NASA Discipline Life Support Systems↗
NASA NTRS1996

Fluid Creep Effects on Near-Wall Solute Transport for Non-Isothermal Ampoules

There is a growing practical and theoretical interest in developing accurate macroscopic modelling for flows arising in chemical or physical vapor transport (VT) crystal growth experiments, including those conducted in reduced gravity environments. Rosner was the first person to point out that previously neglected rarefield gas dynamics phenomena (Stefan and bouyancy-driven flows) become rather important sources of convection. In particular, the combination of rarefaction and strong gradients of temperature (and/or concentration) tangential to the side-walls of the ampoule induces convective flows known as thermal (and concentration) 'creep' respectively. His order-of-magnitude estimates revealed that thermal creep effects can be non-negligible even at normal gravitational levels. On the macroscopic level, the bulk fluid mechanics can be adequately described by the familiar macroscopic equations as long as the boundary conditions are modified to account for the integrated effect of kinetic boundary layers adjacent to solid boundaries. Motivated by the growing importance of these phenomena, we have embarked on a series of computational studies to elucidate these fundamental creep-induced effects for a rarefied gas in simple, two-dimensional confined geometries. However, unlike previous related studies, we resort to a microscopic description of the gas, mathematically expressed by the Boltzmann integro-differential equation. We employ the direct simulation Monte Carlo (DSMC) method of Bird, the theoretical foundations and several practical applications. In the case of thermally induced flows, the no-time counter method of Bird is used, as implemented for a hard-sphere gas. The scheme has been also extended to account for realistic molecular interaction models, an extension necessary if the diffusion physics underlying concentration creep are to be captured.

Papadopoulos, Dimitrios↗
NASA NTRS1997

Adsorption and solvation of ethanol at the water liquid-vapor interface: a molecular dynamics study

The free energy profiles of methanol and ethanol at the water liquid-vapor interface at 310K were calculated using molecular dynamics computer simulations. Both alcohols exhibit a pronounced free energy minimum at the interface and, therefore, have positive adsorption at this interface. The surface excess was computed from the Gibbs adsorption isotherm and was found to be in good agreement with experimental results. Neither compound exhibits a free energy barrier between the bulk and the surface adsorbed state. Scattering calculations of ethanol molecules from a gas phase thermal distribution indicate that the mass accommodation coefficient is 0.98, and the molecules become thermalized within 10 ps of striking the interface. It was determined that the formation of the solvation structure around the ethanol molecule at the interface is not the rate-determining step in its uptake into water droplets. The motion of an ethanol molecule in a water lamella was followed for 30 ns. The time evolution of the probability distribution of finding an ethanol molecule that was initially located at the interface is very well described by the diffusion equation on the free energy surface.

NASA Discipline Exobiology↗
NASA NTRS1996

Mechanism of unassisted ion transport across membrane bilayers

To establish how charged species move from water to the nonpolar membrane interior and to determine the energetic and structural effects accompanying this process, we performed molecular dynamics simulations of the transport of Na+ and Cl- across a lipid bilayer located between two water lamellae. The total length of molecular dynamics trajectories generated for each ion was 10 ns. Our simulations demonstrate that permeation of ions into the membrane is accompanied by the formation of deep, asymmetric thinning defects in the bilayer, whereby polar lipid head groups and water penetrate the nonpolar membrane interior. Once the ion crosses the midplane of the bilayer the deformation "switches sides"; the initial defect slowly relaxes, and a defect forms in the outgoing side of the bilayer. As a result, the ion remains well solvated during the process; the total number of oxygen atoms from water and lipid head groups in the first solvation shell remains constant. A similar membrane deformation is formed when the ion is instantaneously inserted into the interior of the bilayer. The formation of defects considerably lowers the free energy barrier to transfer of the ion across the bilayer and, consequently, increases the permeabilities of the membrane to ions, compared to the rigid, planar structure, by approximately 14 orders of magnitude. Our results have implications for drug delivery using liposomes and peptide insertion into membranes.

NASA Discipline Exobiology↗
NASA NTRS1994

Chemical transitions for interstellar C2 and CN in cloud envelopes

Observations were made of absorption from CH, C2, and CN toward moderately reddened stars in Sco, OB2, Ceo OB3, and Taurus/Auriga. For these directions, most of the reddening is associated with a single cloud complex, for example, the rho Ophiuchus molecular cloud, and as a result, the observations probe moderately dense material. When combined with avaliable data for nearby directions, the survey provides the basis for a comprehensive analysis of the chemistry for these species. The chemical transitions affecting C2 and CN in cloud envelopes were analyzed. The depth into a cloud at which a transition takes place was characterized by tau(sub uv), the grain optical depth at 1000 A. One transition at tau(sub uv) approx. = 2, which arises from, the conversion of C(+) into CO, affects the chemistries for both molecules because of the key role this ion plays. A second one involving production terms in the CN chemistry occurs at tau(sub uv) of approx. = 3; neutral reactions which C2 and CH is more important at larger values for tau(sub uv). The transition from photodissociation to chemical destruction takes place at tau(sub uv) approx. = 4.5 for C2 and CN. The observational data for stars in Sco OB2, Cep OB3, and Taurus/Auriga were studied with chemical rate equations containing the most important production and destruction mechanisms. Because the sample of stars in Sco OB2 includes sight lines with A(sub v) ranging from 1-4 mag, sight lines dominated by photochemistry could be analyzed separately from those controlled by gas-phase destruction. The analysis yielded values for two poorly known rate constants for reactions involved in the production of CN; the reactions are C2 + N yields CN + C and C(+) + NH yields all products. The other directions were analyzed with the inferred values. The predicted column densities for C2 and CN agree with the observed values to better than 50%, and in most instances 20%. When combining the estimates for density and temperature derived from chemical modeling and molecular excitation for a specific cloud, such as the rho Ophiuchus molecular cloud, the portion of the cloud envelope probed by C2 and CN absorption was found to be in pressure equilibrium.

Federman, S. R.↗
NASA NTRS1997

Interactions of anesthetics with the water-hexane interface. A molecular dynamics study

The free energy profiles characterizing the transfer of nine solutes across the liquid-vapor interfaces of water and hexane and across the water-hexane interface were calculated from molecular dynamics simulations. Among the solutes were n-butane and three of its halogenated derivatives, as well as three halogenated cyclobutanes. The two remaining molecules, dichlorodifluoromethane and 1,2-dichloroperfluoroethane, belong to series of halo-substituted methanes and ethanes, described in previous studies (J. Chem. Phys. 1996, 104, 3760; Chem. Phys. 1996, 204, 337). Each series of molecules contains structurally similar compounds that differ greatly in anesthetic potency. The accuracy of the simulations was tested by comparing the calculated and the experimental free energies of solvation of all nine compounds in water and in hexane. In addition. the calculated and the measured surface excess concentrations of n-butane at the water liquid-vapor interface were compared. In all cases, good agreement with experimental results was found. At the water-hexane interface, the free energy profiles for polar molecules exhibited significant interfacial minima, whereas the profiles for nonpolar molecules did not. The existence of these minima was interpreted in terms of a balance between the free energy contribution arising from solute-solvent interactions and the work to form a cavity that accommodates the solute. These two contributions change monotonically, but oppositely, across the interface. The interfacial solubilities of the solutes, obtained from the free energy profiles, correlate very well with their anesthetic potencies. This is the case even when the Meyer-Overton hypothesis, which predicts a correlation between anesthetic potency and solubility in oil, fails.

NASA Center ARC↗
NASA NTRS2000

A semiempirical study for the ground and excited states of free-base and zinc porphyrin-fullerene dyads

The ground and excited states of a covalently linked porphyrin-fullerene dyad in both its free-base and zinc forms (D. Kuciauskas et al., J. Phys. Chem. 100 (1996) 15926) have been investigated by semiempirical methods. The excited-state properties are discussed by investigation of the character of the molecular orbitals. All frontier MOs are mainly localized on either the donor or the acceptor subunit. Thus, the absorption spectra of both systems are best described as the sum of the spectra of the single components. The experimentally observed spectra are well reproduced by the theoretical computations. Both molecules undergo efficient electron transfer in polar but not in apolar solvents. This experimental finding is explained theoretically by explicitly considering solvent effects. The tenth excited state in the gas phase is of charge-separated character where an electron is transferred from the porphyrin donor to the fullerene acceptor subunit. This state is stabilized in energy in polar solvents due to its large formal dipole moment. The stabilization energy for an apolar environment such as benzene is not sufficient to lower this state to become the first excited singlet state. Thus, no electron transfer is observed, in agreement with experiment. In a polar environment such as acetonitrile, the charge-separated state becomes the S, state and electron transfer takes place, as observed experimentally. The flexible single bond connecting both the donor and acceptor subunits allows free rotation by ca. +/- 30 degrees about the optimized ground-state conformation. For the charge-separated state this optimized geometry has a maximum dipole moment. The geometry of the charge-separated state thus does not change relatively to the ground-state conformation. The electron-donating properties of porphyrin are enhanced in the zinc derivative due to a reduced porphyrin HOMO-LUMO energy gap. This yields a lower energy for the charge-separated state compared to the free-base dyad.

Bridged Compounds/chemistry↗
NASA NTRS1972

Magnetism, dimensional changes, and magnetic transitions in hydrated cesium manganese chloride

Dimensional changes (strain) along the three principal crystal axes of the antiferromagnet CsMnCl3-2H2O are studied as a function of magnetic field and temperature in the antiferromagnetic, spin flopped, and paramagnetic phases. Changes in dimensions through the phase transitions between the magnetic states are examined. By applying the molecular field model and utilizing all available information, magnetic properties of CsMnCl3-2H2O are determined. The possible usefulness of this material in a magnetic refrigeration cycle is evaluated.

Woollam, J. A.↗
NASA NTRS1972

Gas physics environment of high altitude Jovian entry.

A description of the gas physics environment associated with high-altitude Jupiter entry is reported. Two aspects of environmental analysis are treated. First, limited discussion is devoted to prediction of the heating environment of the probe aeroshell. Prime emphasis is given to the second aspect of the analysis, a description of the gas particle probe interaction phenomena in the rarefied flow regime. Several molecular reemission models have been devised and exercised. Model selection was based upon the desire to bracket the expected reemission characteristics. Consideration was given to examining diffuse reflection as exemplified by the Maxwellian model and lobular, specular reflection as characterized by the Nocilla model. Variation of fundamental input parameters was investigated to determine particle-probe interaction sensitivity. Regardless of neutral species type, results show that the attenuation of the incoming flux of that species by reflected particles is approximately 15 per cent in the stagnation region at 200 km above the cloud tops.

Lefferdo, J. M.↗
NASA NTRS1974

Molecular column densities in selected model atmospheres

From an examination of predicted column densities, the following conclusions were drawn: (1) The SiO ought to be visible in carbon stars which were generated from triple alpha burning, but absent from carbon stars generated from the CNO bi-cycle. (2) Variation in the observed relative strengths of TiO and ZrO is indicative of real differences in the ratio Ti/Zr. (3) The TiO/ZrO ratio shows a small variation as C/O and effective temperature is changed. (4) Column density of silicon dicarbide (SiC2) is sensitive to abundance, temperature, and gravity; hence all relationships between the strength of SiC2 and other stellar parameters will show appreciable scatter. There is however, a substantial luminosity effect present in the SiC2 column densities. (5) Unexpectedly, SiC2 is anti-correlated with C2. (6) The presence of SiC2 in a carbon star eliminates the possibility of these stars having temperatures greater than or equal to 3000 K, or being produced through the CNO bi-cycle.

Johnson, H. R.↗