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At least 253 records · Page 14

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NASA NTRS1986

An ab initio investigation of possible intermediates in the reaction of the hydroxyl and hydroperoxyl radicals

Ab initio quantum chemical techniques have been used to investigate covalently-bonded and hydrogen-bonded species that may be important intermediates in the reaction of hydroxyl and hydroperoxyl radicals. Stable structures of both types were identified. Basic sets of polarized double-zeta quality and large scale configuration interaction wave functions have been utilized. Based upon electronic energies, the covalently-bonded HOOOH species is found to be 26.4 kcal/mol more stable than the OH and HO2 radicals. Similarly, the hydrogen-bonded HO-HO2 species is found to have an electronic energy 4.7 kcal/mol below that of the component radicals, after correction is made for the basis set superposition error. The hydrogen-bonded form is found to be planar, to possess one relatively 'normal' hydrogen bond, and to have lowest energy 3A-prime and 1A-prime states that are essentially degenerate. The 1A-double prime and 3A-double prime excited states produced by rotation of the unpaired OH electron into the molecular plane are found to be very slightly bound.

Jackels, C. F.↗

NASA NTRS1986

World-wide increase in tropospheric methane, 1978-1983

Techniques used to assess methane concentration in the troposphere are described, and data obtained during the period from 1978 to 1983 are presented in detail. Tropospheric methane concentrations in remote locations averaged a yearly world-wide increase of 0.018 + or - 0.002 parts per million by volume (ppmv). Average world-wide tropospheric concentration of methane in dry air was 1.625 ppmv at the end of 1983 measured against an NBS standard certified as 0.97 ppmv. Contributing to this steady increase in methane concentration are increases in the source strengths from cattle and rice fields, which in turn result from CO, CH4 and HO coupling. Among the physical and chemical effects is an increase in greenhouse warming of about 0.04 C per decade.

Blake, D. R.↗

NASA NTRS1986

Responses of a hot film and a pressure probe to acoustic excitation in mean flow

The responses of a hot film sensor and a pressure probe to acoustic excitation in steady flow up to a Mach number of 0.5 were measured and compared with the responses of a microphone, flush mounted in the wall of the flow duct. When compared in terms of fluctuating pressure, the response of the pressure probe was less than that of the wall microphone by about 2.1 dB or less at the 0.5 Mach number, while the response of the ho film probe was as much as 6.0 dB above that of the wall sensor, at the Mach numbers 0.3 and 0.5. In terms of fluctuating Reynolds number, the response of the hot film probe was greater than that of the wall-mounted sensor by at most 5.0 dB at the same Mach numbers. Removing the response contribution from fluctuating temperature in the hot film mathematical model improved the agreement between the two transducer responses for both comparisons.

Jones, M. G.↗

NASA NTRS1985

Stratospheric chemistry

Recent improvements in the data base for the currently identified reactions describing the chemistry of the major families of trace gas species, HO(x), NO(x), ClO(x), and hydrocarbons are assessed. The important coupling reactions between the families are introduced progressively. Chemical aspects such as heterogeneous reactions and reactions of sodium species, the importance of which are not yet completely established, are discussed. Recent attempts to reconcile some of the more unexpected kinetic behavior which has emerged from the extensive experimental studies of key reactions with current reaction rate theory are also examined. The uncertainties in the current kinetic and photochemical data base is given. The prospects for improvement of data for known reactions of atmospheric importance as well as for the identification of gaps in the chemical description of the atmosphere.

Cox, R. A.↗

NASA NTRS1985

Strat-trop exchange

Exchange between the stratosphere and troposphere is important to the chemical composition of both regions. The export of ozone from the stratosphere provides the troposphere with a means of initiating photochemistry. The precursor molecules originating from the planetary surface provide the stratosphere with its chemical feedstock from which the ozone-controlling HO(x), NO(x), and Cl(x) photochemistries are driven. The tropopause is defined both statistically and in a local, synoptic sense by the value P(sub theta) = .000016 K sq m/kg/s, taken from an objective analysis of 8 years of zonal, temporal mean cross sections of potential temperature, wind and potential vorticity.

Tuck, A. F.↗

NASA NTRS1987

The 1-((diorganooxy phosphonyl) methyl)-2,4- and -2,6-diamino benzenes and their derivatives

The 1-((diorganooxy phosphonyl) methyl)-2,4- and -2,6-dinitro- and diamino benzenes are prepared by nitrating an (organo phosphenyl) methyl benzene to produce the dinitro compounds which are then reduced to the diamino compounds. The organo groups (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids (HO)2P(=0)-. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures.

Mikroyannidis, John A.↗

NASA NTRS1986

Growth-induced anisotropy in bismuth - Rare-earth iron garnets

The bismuth-doped rare-earth iron garnets, (R3-x-yBixPby)Fe5O12 (Bi:RIG, R = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y), were prepared under constant growth conditions to investigate the influence of ionic species on the bismuth-based growth-induced uniaxial anisotropy K(u) exp g. The effect of ionic species on growth-induced anisotropy in Bi:RIG was not consistent with the ionic size model of site ordering. In particular, Bi:SmIG, Bi:EuIG, and Bi:TbIG displayed high growth-induced anisotropies, up to 331,000 erg/cu cm at room temperature for x of about 0.5. The temperature dependence of these K(u) exp gs was somewhat higher than that of the well studied Bi:YIG. The site ordering of Bi can be modeled by assuming that small, low-oxygen-coordination BiOw exp +3-2 w melt complexes have a strong site selectivity for small, high-oxygen coordination sites at the growth interface.

Fratello, V. J.↗

NASA NTRS1987

Effective collision strengths for electron impact excitations in S II

Electron impact collision strengths for forbidden, semiforbidden, and allowed transitions in S II calculated using the R-matrix method are presented. Configuration interaction wave functions are used to represent the six target states included in the calculation. At low impact energies the collision strengths are dominated by resonances for several transitions. The contribution from higher partial waves is obtained in the close-coupling approximation with exchange terms omitted. Results are presented for the effective collision strengths over a wide temperature range (5000-150,000 K) of astrophysical interest. The present results for the 4S(0) yields 2P(0) transition are 20-30 percent lower than previous calculations, while for the 4S(0) yields 2D(0) transition they are in good agreement. The results are approximately 30 percent higher than those of Ho and Henry (1983) for the 4S(0) yields 2P(0) transition at 80,000 K, and the difference between the two results increases with decreasing temperatures (under 80,000 K).

Tayal, S. S.↗

NASA NTRS1987

Vertical constituent transport in the mesosphere

Ground-based microwave spectroscopy measurements of mesospheric CO and H2O vertical mixing ratio profiles are used to infer vertical mixing rates in the upper mesosphere. The CO and H2O data consistently imply vertical eddy diffusion coefficients in the 70- to 85-km region of 100,000-200,000 sq cm/s during spring through summer at midlatidues. Although chemical acceleration of vertical transport is substantial for O and O3, below the mesopause, the divergences of their associated fluxes are modest, with at most a factor of 2 effect on the concentrations of O and O3 for measured variability in gravity wave activity. Comparison of Solar Mesosphere Explorer (SME) O3 data with model results reinforces the conclusions of slow vertical mixing in the upper mesosphere as a consequence of the reduced HO(x) catalytic loss of odd oxygen. The changes in chemical rate constants recommended by Rusch and Eckman (1985), in conjunction with slow vertical mixing, yield good agreement with SME O3 data. The slow vertical mixing deduced in this study is consistent with upper limits obtained from studies of the mesospheric heat budget and could be construed as evidence for an advectively controlled mesosphere. A comparison of the vertical eddy diffusion coefficients for momentum stresses, constituent transport, and heat transport suggests that the eddy Prandtl number must be of order 10.

Strobel, Darrell F.↗

NASA NTRS1987

Efficient holmium:yttrium lithium fluoride laser longitudinally pumped by a semiconductor laser array

Optical pumping of a holmium:yttrium lithium floride (Ho:YLF) crystal with a 790-nm continuous-wave diode-laser array has generated 56 mW of 2.1-micron laser radiation with an optical-to-optical conversion slope efficiency of 33 percent while the crystal temperature is held at 77 K. The lasing threshold occurs at 7 mW of input power, and laser operation continues up to a crystal temperature of 124 K.

Hemmati, H.↗

NASA NTRS1988

Ground-based column abundance measurements of atmospheric hydroxyl

The preliminary results of ground-based OH column abundance measurements from Truk, Federated States of Micronesia, are contained. These are the first OH column measurements from the tropics, and constitute a signficcant contribution to the OH data base. Comparisons of tropical OH behavior with the extensive mid-latitude observations serve as a critical test of the current understanding of the HO (sub x) photochemistry and its relationship to the other major chemical families. The quasi-biennial oscillation (QBO) in tropical stratospheric winds exerts a major influence on the Hadley cell vertical transport. Related QBOs in total O3 and in stratospheric H2O were identified, but QBO effects on other stratospheric species are still unknown. The solar tide in the tropics produces a diurnal surface pressure variation of 2 to 3 mb; its effect on OH photochemistry in the stratosphere may be significant.

Burnett, Clyde R.↗

NASA NTRS1988

Growth and characterization of materials for tunable lasers in the near infrared spectral region

During this reporting period, work proceeded in two directions. The first was the development of crystal growth procedures for rare earth doped LiYF4 crystals. The procedures for growth and pre-growth treatment of starting materials for undoped LiYF4 crystals were established and good optical quality materials were grown. A significant amount of time was spent trying to establish the optimum growth parameters for Yb(3+)-doped crystals. Unfortunately, it has proven difficult to obtain large size boules of high optical quality crystals of LiYF4 with doping concentrations of Yb(3+) of several percent. Because of these problems, this research is to be changed to attempt doping with other trivalent rare earth ions such as Ho, Er, and Tm. The second research area was investigating the potential of LiNbO3:Mg,Cr and LiNbO3:Mg,Cr,Yb as possible laser materials. The results are summarized.

Powell, Richard C.↗

NASA NTRS1987

Outer magnetospheric fluctuations and pulsar timing noise

The Cheng, Ho, and Ruderman (1986) outer-magnetosphere gap model was used to investigate the stability of Crab-type outer magnetosphere gaps for pulsars having the parameter (Omega-square B) similar to that of the Crab pulsar. The Lamb, Pines, and Shaham (1978) fluctuating magnetosphere noise model was applied to the Crab pulsar to examine the type of the equation of state that best describes the structure of the neutron star. The noise model was also applied to other pulsars, and the theoretical results were compared with observational data. The results of the comparison are consistent with the stiff equation of state, as suggested by the vortex creep model of the neutron star interior. The timing-noise observations also contribute to the evidence for the existence of superfluid in the core of the neutron star.

Cheng, K. S.↗

NASA NTRS1988

Effect of computed horizontal diffusion coefficients on two-dimensional N2O model distributions

The effects of horizontal diffusion coefficients K(yy) and K(yz), computed directly from the residual circulation, on the N2O distribution in a photochemical model were investigated, using a modified version of the two-dimensional model of Guthrie et al. (1984). The residual circulation was computed using the NMC's temperature data and the heating rates reported by Rosenfield et al. (1987). As compared with the effect of the residual circulation alone, the use of horizontal diffusion coefficients produced substantial changes in the N2O distribution and increased the N2O's lifetime values by a few percent. It is suggested that trace gases, such as CH4, CFCl3, CF2Cl2, CH3Cl, and CCl4, which impact the NO(x), HO(x), and Cl(x) radical distributions and therefore ozone, will be influenced in a similar manner by the addition of more realistic diffusion fields.

Jackman, Charles H.↗

NASA NTRS1988

Development of mid-infrared solid state lasers for spaceborne lidar

This semiannual progress report covers work performed during the period from April 13, 1988 to October 13, 1988 under NASA grant number NAG-1-877 entitled, Development of mid-infrared solid state lasers for spaceborne lidar. We have designed a flashlamp-pumped Cr3(+);GSAG laser of pulsed laser energy greater than 200 mJ and of pulse width of 1 ms FWHM to simulate a high-power laser diode in pumping mid-infrared laser crystals such as Tm3(+), Er3(+), and/or Ho3(+)-ion doped YAG, YLF or other host materials. This Cr3(+);GSAG laser will be used to determine optimum conditions for laser diode pumped mid-infrared lasers, maximum energy extraction limit with longitudinal pumping, thermal damage limit, and other problems related to high power laser diode pumping. We have completed a modification of an existing flashlamp-pumped and liquid nitrogen cooled rare earth laser system for 60 J electrical input energy and a 500 micron pulse width, and have carried out preliminary experiments with a Ho(+):Er3(+):Tm3(+):YAG crystal to test the system performance. This flashlamp-pumped rare earth laser system will be used to determine optimum Tm3(+)-ion concentration in Ho3(+):Cr3(+):Tm3(+):YAG crystal in the remaining research period.

Whitney, Donald A.↗

NASA NTRS1988

Formation of polar stratospheric clouds simulated in a two dimensional model of the atmosphere

A microphysics code has been implemented in a two dimensional model of the atmosphere to study formation of polar stratospheric clouds containing HCl or HNO3. The model range is from pole to pole in latitude and from the ground to about 20 km in altitude. Resolution in latitude is 10 deg and about 0.8 km in altitude. This is an Eulerian model with prescribed eddy diffusion coefficients and the circulation obtained from observations. The chemistry of the model follows the family approach for NO(x), Cl(x) and HO(x) while the ozone is fixed and changed seasonally. The aerosol code is based on an assigned population of condensation, coagulation and sedimentation. Aerosol growth is simulated in nine different size bins ranging between 0.01u and 2.56u. The model has been built to study aerosol layers formation in the upper troposphere and lower stratosphere and has been validated for sulfate aerosol resulting from a rather complex sulfur chemistry.

Visconti, Guido↗

NASA NTRS1988

Windshear detection and avoidance - Airborne systems perspective

The generalized windshear hazard index presently defined is derived from aircraft-position wind data and remotely sensed data obtained along the extended flight path by such candidate sensor technologies as microwave Doppler radar, Doppler lidar, and IR radiometry. Attention is given here to the results of a comparative evaluation of CO2 and Ho:YAG lidar sensor-employing windshear-detection systems, over a range 1-3 km ahead of the aircraft (corresponding to 15-45 sec of warning time). While the technology for a 10.6-micron CO2 lidar system is available, an optimum 2-micron REE laser crystal-based system remains to be developed.

Bowles, Roland L.↗

NASA NTRS1988

Windshear avoidance - Requirements and proposed system for airborne lidar detection

A generalized windshear hazard index is derived from considerations of wind conditions and an aircraft's present and potential altitude. Based on a systems approach to the windshear threat, lidar appears to be a viable methodology for windshear detection and avoidance, even in conditions of moderately heavy precipitation. The airborne CO2 and Ho:YAG lidar windshear detection systems analyzed can each give the pilot information about the line-of-sight component of windshear threat from his present position to a region extending 1 to 3 km in front of the aircraft. This constitutes a warning time of 15 to 45 s. The technology necessary to design, build and test such a brassboard 10.6-micron CO2 lidar is at hand.

Targ, Russell↗