Absolute rate coefficients for photorecombination of beryllium-like and boron-like silicon ions
NASA Astrophysics Data System (ADS)
Bernhardt, D.; Becker, A.; Brandau, C.; Grieser, M.; Hahn, M.; Krantz, C.; Lestinsky, M.; Novotný, O.; Repnow, R.; Savin, D. W.; Spruck, K.; Wolf, A.; Müller, A.; Schippers, S.
2016-04-01
We report measured rate coefficients for electron-ion recombination of Si10+ forming Si9+ and of Si9+ forming Si8+, respectively. The measurements were performed using the electron-ion merged-beams technique at a heavy-ion storage ring. Electron-ion collision energies ranged from 0 to 50 eV for Si9+ and from 0 to 2000 eV for Si10+, thus, extending previous measurements for Si10+ (Orban et al 2010 Astrophys. J. 721 1603) to much higher energies. Experimentally derived rate coefficients for the recombination of Si9+ and Si10+ ions in a plasma are presented along with simple parameterizations. These rate coefficients are useful for the modeling of the charge balance of silicon in photoionized plasmas (Si9+ and Si10+) and in collisionally ionized plasmas (Si10+ only). In the corresponding temperature ranges, the experimentally derived rate coefficients agree with the latest corresponding theoretical results within the experimental uncertainties.
NASA Astrophysics Data System (ADS)
Badnell, N. R.; Spruck, K.; Krantz, C.; Novotný, O.; Becker, A.; Bernhardt, D.; Grieser, M.; Hahn, M.; Repnow, R.; Savin, D. W.; Wolf, A.; Müller, A.; Schippers, S.
2016-05-01
Experimentally measured and theoretically calculated rate coefficients for the recombination of W19 +([Kr ] 4 d10 4 f9 ) ions with free electrons (forming W18 +) are presented. At low electron-ion collision energies, the merged-beam rate coefficient is dominated by strong, mutually overlapping, recombination resonances as already found previously for the neighboring charge-state ions W18 + and W20 +. In the temperature range where W19 + is expected to form in a collisionally ionized plasma, the experimentally derived recombination rate coefficient deviates by up to a factor of about 20 from the theoretical rate coefficient obtained from the Atomic Data and Analysis Structure database. The present calculations, which employ a Breit-Wigner redistributive partitioning of autoionizing widths for dielectronic recombination via multi-electron resonances, reproduce the experimental findings over the entire temperature range.
Teplukhin, Alexander; Babikov, Dmitri
2016-07-28
Rigorous calculations of scattering resonances in ozone are carried out for a broad range of rotational excitations. The accurate potential energy surface of Dawes is adopted, and a new efficient method for calculations of ro-vibrational energies, wave functions and resonance lifetimes is employed (which uses hyper-spherical coordinates, the sequential diagonalization/truncation approach, grid optimization and complex absorbing potential). A detailed analysis is carried out to characterize distributions of resonance energies and lifetimes, their rotational/vibrational content and their positions with respect to the centrifugal barrier. Emphasis is on the contribution of these resonances to the recombination process that forms ozone. It is found that major contributions come from localized resonances at energies near the top of the barrier. Delocalized resonances at higher energies should also be taken into account, while very narrow resonances at low energies (trapped far behind the centrifugal barrier) should be treated as bound states. The absolute value of the recombination rate coefficient, its pressure and temperature dependencies are obtained using the energy-transfer model developed in the earlier work. Good agreement with experimental data is obtained if one follows the suggestion of Troe, who argued that the energy transfer mechanism of recombination is responsible only for 55% of the recombination rate (with the remaining 45% coming from the competing chaperon mechanism). PMID:27364351
Determination of absolute internal conversion coefficients using the SAGE spectrometer
NASA Astrophysics Data System (ADS)
Sorri, J.; Greenlees, P. T.; Papadakis, P.; Konki, J.; Cox, D. M.; Auranen, K.; Partanen, J.; Sandzelius, M.; Pakarinen, J.; Rahkila, P.; Uusitalo, J.; Herzberg, R.-D.; Smallcombe, J.; Davies, P. J.; Barton, C. J.; Jenkins, D. G.
2016-03-01
A non-reference based method to determine internal conversion coefficients using the SAGE spectrometer is carried out for transitions in the nuclei of 154Sm, 152Sm and 166Yb. The Normalised-Peak-to-Gamma method is in general an efficient tool to extract internal conversion coefficients. However, in many cases the required well-known reference transitions are not available. The data analysis steps required to determine absolute internal conversion coefficients with the SAGE spectrometer are presented. In addition, several background suppression methods are introduced and an example of how ancillary detectors can be used to select specific reaction products is given. The results obtained for ground-state band E2 transitions show that the absolute internal conversion coefficients can be extracted using the methods described with a reasonable accuracy. In some cases of less intense transitions only an upper limit for the internal conversion coefficient could be given.
Absolute magnitudes and phase coefficients of trans-Neptunian objects
NASA Astrophysics Data System (ADS)
Alvarez-Candal, A.; Pinilla-Alonso, N.; Ortiz, J. L.; Duffard, R.; Morales, N.; Santos-Sanz, P.; Thirouin, A.; Silva, J. S.
2016-02-01
Context. Accurate measurements of diameters of trans-Neptunian objects (TNOs) are extremely difficult to obtain. Thermal modeling can provide good results, but accurate absolute magnitudes are needed to constrain the thermal models and derive diameters and geometric albedos. The absolute magnitude, HV, is defined as the magnitude of the object reduced to unit helio- and geocentric distances and a zero solar phase angle and is determined using phase curves. Phase coefficients can also be obtained from phase curves. These are related to surface properties, but only few are known. Aims: Our objective is to measure accurate V-band absolute magnitudes and phase coefficients for a sample of TNOs, many of which have been observed and modeled within the program "TNOs are cool", which is one of the Herschel Space Observatory key projects. Methods: We observed 56 objects using the V and R filters. These data, along with those available in the literature, were used to obtain phase curves and measure V-band absolute magnitudes and phase coefficients by assuming a linear trend of the phase curves and considering a magnitude variability that is due to the rotational light-curve. Results: We obtained 237 new magnitudes for the 56 objects, six of which were without previously reported measurements. Including the data from the literature, we report a total of 110 absolute magnitudes with their respective phase coefficients. The average value of HV is 6.39, bracketed by a minimum of 14.60 and a maximum of -1.12. For the phase coefficients we report a median value of 0.10 mag per degree and a very large dispersion, ranging from -0.88 up to 1.35 mag per degree.
Absolute rates of hole transfer in DNA.
Senthilkumar, Kittusamy; Grozema, Ferdinand C; Guerra, Célia Fonseca; Bickelhaupt, F Matthias; Lewis, Frederick D; Berlin, Yuri A; Ratner, Mark A; Siebbeles, Laurens D A
2005-10-26
Absolute rates of hole transfer between guanine nucleobases separated by one or two A:T base pairs in stilbenedicarboxamide-linked DNA hairpins were obtained by improved kinetic analysis of experimental data. The charge-transfer rates in four different DNA sequences were calculated using a density-functional-based tight-binding model and a semiclassical superexchange model. Site energies and charge-transfer integrals were calculated directly as the diagonal and off-diagonal matrix elements of the Kohn-Sham Hamiltonian, respectively, for all possible combinations of nucleobases. Taking into account the Coulomb interaction between the negative charge on the stilbenedicarboxamide linker and the hole on the DNA strand as well as effects of base pair twisting, the relative order of the experimental rates for hole transfer in different hairpins could be reproduced by tight-binding calculations. To reproduce quantitatively the absolute values of the measured rate constants, the effect of the reorganization energy was taken into account within the semiclassical superexchange model for charge transfer. The experimental rates could be reproduced with reorganization energies near 1 eV. The quantum chemical data obtained were used to discuss charge carrier mobility and hole-transport equilibria in DNA. PMID:16231945
The Absolute Rate of LGRB Formation
NASA Astrophysics Data System (ADS)
Graham, J. F.; Schady, P.
2016-06-01
We estimate the long-duration gamma-ray burst (LGRB) progenitor rate using our recent work on the effects of environmental metallically on LGRB formation in concert with supernovae (SNe) statistics via an approach patterned loosely off the Drake equation. Beginning with the cosmic star formation history, we consider the expected number of broad-line Type Ic events (the SNe type associated with LGRBs) that are in low-metallicity host environments adjusted by the contribution of high-metallicity host environments at a much reduced rate. We then compare this estimate to the observed LGRB rate corrected for instrumental selection effects to provide a combined estimate of the efficiency fraction of these progenitors to produce LGRBs and the fraction of which are beamed in our direction. From this we estimate that an aligned LGRB occurs for approximately every 4000 ± 2000 low-metallically broad-lined SNe Ic. Therefore, if one assumes a semi-nominal beaming factor of 100, then only about one such supernova out of 40 produce an LGRB. Finally, we propose an off-axis LGRB search strategy of targeting only broad-line Type Ic events that occur in low-metallicity hosts for radio observation.
Experimental Mg IX photorecombination rate coefficient
NASA Astrophysics Data System (ADS)
Schippers, S.; Schnell, M.; Brandau, C.; Kieslich, S.; Müller, A.; Wolf, A.
2004-07-01
The rate coefficient for radiative and dielectronic recombination of beryllium-like magnesium ions was measured with high resolution at the Heidelberg heavy-ion storage ring TSR. In the electron-ion collision energy range 0-207 eV resonances due to 2s -> 2p (Δ N = 0) and 2s -> 3l (Δ N=1) core excitations were detected. At low energies below 0.15 eV the recombination rate coefficient is dominated by strong 1s2 (2s 2p 3P) 7l resonances with the strongest one occuring at an energy of only 21 meV. These resonances decisively influence the Mg IX recombination rate coefficient in a low temperature plasma. The experimentally derived Mg IX dielectronic recombination rate coefficient (±15% systematical uncertainty) is compared with the recommendation by Mazzotta et al. (1998, A&AS, 133, 403) and the recent calculations by Gu (2003, ApJ, 590, 1131) and by Colgan et al. (2003, A&A, 412, 597). These results deviate from the experimental rate coefficient by 130%, 82% and 25%, respectively, at the temperature where the fractional abundance of Mg IX is expected to peak in a photoionized plasma. At this temperature a theoretical uncertainty in the 1s2 (2s 2p 3P) 7l resonance positions of only 100 meV would translate into an uncertainty of the plasma rate coefficient of almost a factor 3. This finding emphasizes that an accurate theoretical calculation of the Mg IX recombination rate coefficient from first principles is challenging.
Determination of RW3-to-water mass-energy absorption coefficient ratio for absolute dosimetry.
Seet, Katrina Y T; Hanlon, Peta M; Charles, Paul H
2011-12-01
The measurement of absorbed dose to water in a solid-phantom may require a conversion factor because it may not be radiologically equivalent to water. One phantom developed for the use of dosimetry is a solid water, RW3 white-polystyrene material by IBA. This has a lower mass-energy absorption coefficient than water due to high bremsstrahlung yield, which affects the accuracy of absolute dosimetry measurements. In this paper, we demonstrate the calculation of mass-energy absorption coefficient ratios, relative to water, from measurements in plastic water and RW3 with an Elekta Synergy linear accelerator (6 and 10 MV photon beams) as well as Monte Carlo modeling in BEAMnrc and DOSXYZnrc. From this, the solid-phantom-to-water correction factor was determined for plastic water and RW3. PMID:21960410
Flow rate calibration for absolute cell counting rationale and design.
Walker, Clare; Barnett, David
2006-05-01
There is a need for absolute leukocyte enumeration in the clinical setting, and accurate, reliable (and affordable) technology to determine absolute leukocyte counts has been developed. Such technology includes single platform and dual platform approaches. Derivations of these counts commonly incorporate the addition of a known number of latex microsphere beads to a blood sample, although it has been suggested that the addition of beads to a sample may only be required to act as an internal quality control procedure for assessing the pipetting error. This unit provides the technical details for undertaking flow rate calibration that obviates the need to add reference beads to each sample. It is envisaged that this report will provide the basis for subsequent clinical evaluations of this novel approach. PMID:18770842
Nanoscale Thermoelectrics: A Study of the Absolute Seebeck Coefficient of Thin Films
NASA Astrophysics Data System (ADS)
Mason, Sarah J.
measure, S, as a function of temperature using a micro-machined thermal isolation platform consisting of a suspended, patterned SiN membrane. By measuring a series of thicknesses of metallic films up to the infinitely thin film limit, in which the electrical resistivity is no longer decreasing with increasing film thickness, but still not at bulk values, along with the effective electron mean free path, we are able to show the contribution of the leads needed to measure this property. Having a comprehensive understanding of the background contribution we are able to determine the absolute Seebeck coefficient of a wide variety of thin films. The nature of the design of the SiN membrane also allows the ability to accurately and directly measure thermal and electrical transport of the thin films yielding a comprehensive measurement of the three quantities that characterize a material's efficiency. This can serve to further the development of thermoelectric materials through precise measurements of the material properties that dictate efficiency.
Experimental electron-impact excitation rate coefficients for lithium-like Si XII
NASA Astrophysics Data System (ADS)
König, R.; Kolk, K.-H.; Kunze, H.-J.
1993-07-01
Absolute excitation rate coefficients have been determined experimentally for all excited states up to 1s25f of the lithium-like ion Si XII using a well diagnosed theta-pinch plasma. A new method has been developed to determine the most crucial quantity of these measurements, the absolute concentration of the silicon ions in the plasma. For this we made use of the fact that sufficiently high lying levels are in partial local thermodynamic equilibrium (PLTE) with the ground state of the next higher ionization stage. A theoretical population model has been developed to study the influence of the different processes that might contribute to the population of the different levels at our plasma parameters. For most levels the theoretical excitation rate coefficients were found to be in fair agreement with the theoretical ones. The error of the experimentally determined excitation rate coefficients is of the order of ±50%.
Excitation rate coefficient measurements of Cu xiii and Cu xvii ions
NASA Astrophysics Data System (ADS)
Datla, R. U.; Roberts, J. R.; Rowan, W. L.; Mann, J. B.
1986-12-01
The absolute excitation rate coefficients for Cu xiii and Cu xvii optically allowed transitions have been measured using the Texas Experimental Tokamak (TEXT) tokamak. Cu is injected by the laser-ablation method at a time when the plasma has attained steady-state temperature and density profiles. The absolute intensities of the magnetic-dipole-forbidden transitions within the Cu xiii 3s23p5 and the Cu xvii 3s23p ground configurations are measured. The intensities of optically allowed vacuum-ultraviolet lines within the 3p43d-3p5 transition array of Cu xiii and within the 3d-3p transition array of Cu xvii are measured with a 2.2-m grazing incidence spectrometer. This instrument is radiometrically calibrated in situ by using the branching-ratio technique. The absolute excitation rate coefficients are deduced from these measurements, assuming coronal equilibrium, optically thin line emission, and statistical population within the ground configuration. The experimental rate coefficients for these transition arrays are found to be 2.84×10-8 cm3 s-1 for Cu xiii at an electron temperature of 127 eV and 3.5×10-8 cm3 s-1 for Cu xvii at an electron temperature of 240 eV. These results are in good agreement with excitation rate coefficients computed in a distorted-wave approximation. The estimated uncertainty in the experimental values is +/-70%.
Experimental Excitation Rate Coefficients for Ne VIII Ions
NASA Astrophysics Data System (ADS)
Chang, C. C.; Greve, P.; Kolk, K.-H.; Kunze, H.-J.
1984-02-01
From the line emission of a pure neon plasma produced in a theta pinch discharge rate coefficients for the excitation of the n = 3 and 4 levels in Ne VIII ions are derived and compared with theoretical calculations and previous measurements. The general agreement between theory and all measurements is rather satisfactory for the excitation to the n = 3 levels, the measured rate coefficients to the 4p and 4d levels, however, being consistently too low.
RECOMBINATION RATE COEFFICIENTS OF BORON-LIKE Ne
Mahmood, S.; Orban, I.; Ali, S.; Schuch, R.; Glans, P.; Bleda, E. A.; Altun, Z.
2013-07-10
Recombination of Ne{sup 5+} was measured in a merged-beam type experiment at the heavy-ion storage ring CRYRING. In the collision energy range 0-110 eV resonances due to 2s {sup 2}2p {yields} 2s2p {sup 2} ({Delta}n = 0) and 2s {sup 2}2p {yields} 2s {sup 2}3l ({Delta}n = 1), core excitations were observed. The experimentally derived rate coefficients agree well with the calculations obtained using AUTOSTRUCTURE. At low energies, recombination is dominated by resonances belonging to the spin-forbidden 2s2p {sup 2}({sup 4} P{sub J})nl series. The energy-dependent rate coefficients were convoluted with a Maxwell-Boltzmann electron energy distribution to obtain plasma recombination rate coefficients. The data from the literature deviate from the measured results at low temperature.
RECOMBINATION RATE COEFFICIENTS OF Be-LIKE Si
Orban, I.; Boehm, S.; Schuch, R.; Loch, S. D.
2010-10-01
Recombination of Be-like Si{sup 10+} over the 0-43 eV electron-ion energy range is measured at the CRYRING electron cooler. In addition to radiative and dielectronic recombination, the recombination spectrum also shows strong contributions from trielectronic recombination. Below 100 meV, several very strong resonances associated with a spin-flip of the excited electron dominate the spectrum and also dominate the recombination in the photoionized plasma. The resonant plasma rate coefficients corrected for the experimental field ionization are in good agreement with calculated results by Gu and with AUTOSTRUCTURE calculations. All other calculations significantly underestimate the plasma rate coefficients at low temperatures.
ROVIBRATIONAL QUENCHING RATE COEFFICIENTS OF HD IN COLLISIONS WITH He
Nolte, J. L.; Stancil, P. C.; Lee, T.-G.; Balakrishnan, N.; Forrey, R. C. E-mail: stancil@physast.uga.edu E-mail: naduvala@unlv.nevada.edu
2012-01-01
Along with H{sub 2}, HD has been found to play an important role in the cooling of the primordial gas for the formation of the first stars and galaxies. It has also been observed in a variety of cool molecular astrophysical environments. The rate of cooling by HD molecules requires knowledge of collisional rate coefficients with the primary impactors, H, He, and H{sub 2}. To improve knowledge of the collisional properties of HD, we present rate coefficients for the He-HD collision system over a range of collision energies from 10{sup -5} to 5 Multiplication-Sign 10{sup 3} cm{sup -1}. Fully quantum mechanical scattering calculations were performed for initial HD rovibrational states of j = 0 and 1 for v = 0-17 which utilized accurate diatom rovibrational wave functions. Rate coefficients of all {Delta}v = 0, -1, and -2 transitions are reported. Significant discrepancies with previous calculations, which adopted a small basis and harmonic HD wave functions for excited vibrational levels, were found for the highest previously considered vibrational state of v = 3. Applications of the He-HD rate coefficients in various astrophysical environments are briefly discussed.
Experimental electron-impact excitation rate coefficients for beryllium-like Si XI
NASA Astrophysics Data System (ADS)
König, R.; Kolk, K.-H.; Kunze, H.-J.
1996-06-01
Absolute excitation rate coefficients for a large number of levels (up to n = 4) of the singlet and triplet system of Si XI have been experimentally determined in a well-diagnosed theta-pinch plasma with the plasma spectroscopic method. The population of the metastable triplet ground state has been derived from the intensity of the intercombination line. A theoretical population model has been developed to investigate whether collisional coupling of the levels and cascading affected the measurements. The model has also been used to calculate line intensity ratios of strongly density or temperature dependent line pairs which can be used for plasma diagnostic purposes. The measured effective excitation rate coefficients are accurate to about ±50%. All of them, apart from the value for the 2s4s 3S1 level, agreed within the error margins with existing theoretical data.
Gas-phase rate coefficients of the reaction of ozone with four sesquiterpenes at 295 ± 2 K.
Richters, Stefanie; Herrmann, Hartmut; Berndt, Torsten
2015-05-01
The rate coefficients of the reaction of ozone with the four atmospherically relevant sesquiterpenes β-caryophyllene, α-humulene, α-cedrene and isolongifolene were investigated at 295 ± 2 K and atmospheric pressure by at least two independent experimental investigations for each reaction. Relative rate experiments were carried out in a flow tube using two different experimental approaches with GC-MS detection (RR 1) and PTR-MS analysis (RR 2) as the analytical techniques. Absolute rate coefficients were determined in a stopped-flow experiment following the ozone depletion by means of UV spectroscopy. The average rate coefficients from the combined investigations representing the mean values of the different experimental methods are (unit: cm(3) molecule(-1) s(-1)): k(O3+β-caryophyllene) = (1.1 ± 0.3) × 10(-14) (methods: RR 1, RR 2, absolute), k(O3+α-humulene) = (1.2 ± 0.3) × 10(-14) (RR 1, RR 2), k(O3+α-cedrene) = (1.7 ± 0.5) × 10(-16) (RR 2, absolute) and k(O3+isolongifolene) = (1.1 ± 0.5) × 10(-17) (RR 2, absolute). The high ozonolysis rate coefficients for β-caryophyllene and α-humulene agree well with the results by Shu and Atkinson (Int. J. Chem. Kinet., 1994, 26) and lead to short atmospheric lifetimes of about two minutes with respect to the ozone reaction. The relatively small rate coefficients for α-cedrene and isolongifolene differ from the available literature values by a factor of about 2.5-6. Possible reasons for the deviations are discussed. Finally, calibrated sesquiterpene FT-IR spectra were recorded for the first time. PMID:25866852
McLean, A P; Blampied, N M
2001-01-01
Twelve pigeons responded on two keys under concurrent variable-interval (VI) schedules. Over several series of conditions, relative and absolute magnitudes of reinforcement were varied. Within each series, relative rate of reinforcement was varied and sensitivity of behavior ratios to reinforcer-rate ratios was assessed. When responding at both alternatives was maintained by equal-sized small reinforcers, sensitivity to variation in reinforcer-rate ratios was the same as when large reinforcers were used. This result was observed when the overall rate of reinforcement was constant over conditions, and also in another series of concurrent schedules in which one schedule was kept constant at VI ached 120 s. Similarly, reinforcer magnitude did not affect the rate at which response allocation approached asymptote within a condition. When reinforcer magnitudes differred between the two responses and reinforcer-rate ratios were varied, sensitivity of behavior allocation was unaffected although response bias favored the schedule that arranged the larger reinforcers. Analysis of absolute response rates ratio sensitivity to reinforcement occurrred on the two keys showed that this invariance of response despite changes in reinforcement interaction that were observed in absolute response rates on the constant VI 120-s schedule. Response rate on the constant VI 120-s schedule was inversely related to reinforcer rate on the varied key and the strength of this relation depended on the relative magnitude of reinforcers arranged on varied key. Independence of sensitivity to reinforcer-rate ratios from relative and absolute reinforcer magnitude is consistent with the relativity and independence assumtions of the matching law. PMID:11256865
Absolute and Relative Reliability of Percentage of Syllables Stuttered and Severity Rating Scales
ERIC Educational Resources Information Center
Karimi, Hamid; O'Brian, Sue; Onslow, Mark; Jones, Mark
2014-01-01
Purpose: Percentage of syllables stuttered (%SS) and severity rating (SR) scales are measures in common use to quantify stuttering severity and its changes during basic and clinical research conditions. However, their reliability has not been assessed with indices measuring both relative and absolute reliability. This study was designed to provide…
FFTF (Fast Flux Test Facility) Reactor Characterization Program: Absolute Fission-rate Measurements
Fuller, J.L.; Gilliam, D.M.; Grundl, J.A.; Rawlins, J.A.; Daughtry, J.W.
1981-05-01
Absolute fission rate measurements using modified National Bureau of Standards fission chambers were performed in the Fast Flux Test Facility at two core locations for isotopic deposits of {sup 232}Th, {sup 233}U, {sup 235}U, {sup 238}U, {sup 237}Np, {sup 239}Pu, {sup 240}Pu, and {sup 241}Pu. Monitor chamber results at a third location were analyzed to support other experiments involving passive dosimeter fission rate determinations.
FFTF (FAST FLUX TEST FACILITY) REACTOR CHARACTERIZATION PROGRAM ABSOLUTE FISSION RATE MEASUREMENTS
FULLER JL; GILLIAM DM; GRUNDL JA; RAWLINS JA; DAUGHTRY JW
1981-05-01
Absolute fission rate measurements using modified National Bureau of Standards fission chambers were performed in the Fast Flux Test Facility at two core locations for isotopic deposits of {sup 232}Th, {sup 233}U, {sup 235}U, {sup 238}U, {sup 237}Np, {sup 239}Pu, {sup 240}Pu, and {sup 241}Pu. Monitor chamber results at a third location were analyzed to support other experiments involving passive dosimeter fission rate determinations.
Szabó, Milán; Wangpraseurt, Daniel; Tamburic, Bojan; Larkum, Anthony W D; Schreiber, Ulrich; Suggett, David J; Kühl, Michael; Ralph, Peter J
2014-10-01
Pulse Amplitude Modulation (PAM) fluorometry has been widely used to estimate the relative photosynthetic efficiency of corals. However, both the optical properties of intact corals as well as past technical constrains to PAM fluorometers have prevented calculations of the electron turnover rate of PSII. We used a new Multi-colour PAM (MC-PAM) in parallel with light microsensors to determine for the first time the wavelength-specific effective absorption cross-section of PSII photochemistry, σII(λ), and thus PAM-based absolute electron transport rates of the coral photosymbiont Symbiodinium both in culture and in hospite in the coral Pocillopora damicornis. In both cases, σII of Symbiodinium was highest in the blue spectral region and showed a progressive decrease towards red wavelengths. Absolute values for σII at 440 nm were up to 1.5-times higher in culture than in hospite. Scalar irradiance within the living coral tissue was reduced by 20% in the blue when compared to the incident downwelling irradiance. Absolute electron transport rates of P. damicornis at 440 nm revealed a maximum PSII turnover rate of ca. 250 electrons PSII(-1) s(-1), consistent with one PSII turnover for every 4 photons absorbed by PSII; this likely reflects the limiting steps in electron transfer between PSII and PSI. Our results show that optical properties of the coral host strongly affect light use efficiency of Symbiodinium. Therefore, relative electron transport rates do not reflect the productivity rates (or indeed how the photosynthesis-light response is parameterised). Here we provide a non-invasive approach to estimate absolute electron transport rates in corals. PMID:25146689
Temperature Dependence of the O + HO2 Rate Coefficient
NASA Technical Reports Server (NTRS)
Nicovich, J. M.; Wine, P. H.
1997-01-01
A pulsed laser photolysis technique has been employed to investigate the kinetics of the radical-radical reaction O((sup 3)P) + HO2 OH + O2 over the temperature range 266-391 K in 80 Torr of N2 diluent gas. O((sup 3)P) was produced by 248.5-nm KrF laser photolysis of O3 followed by rapid quenching of O(1D) to O((sup 3)P) while HO2 was produced by simultaneous photolysis of H2O2 to create OH radicals which, in turn, reacted with H2O2 to yield HO2. The O((sup 3)P) temporal profile was monitored by using time-resolved resonance fluorescence spectroscopy. The HO2 concentration was calculated based on experimentally measured parameters. The following Arrhenius expression describes our experimental results: k(sub 1)(T) equals (2.91 +/- 0.70) x 10(exp -11) exp[(228 +/- 75)/T] where the errors are 2 sigma and represent precision only. The absolute uncertainty in k, at any temperature within the range 266-391 K is estimated to be +/- 22 percent. Our results are in excellent agreement with a discharge flow study of the temperature dependence of k(sub 1) in 1 Torr of He diluent reported by Keyser, and significantly reduce the uncertainty in the rate of this important stratospheric reaction at subambient temperatures.
Extended Simulations of Graphene Growth with Updated Rate Coefficients
Whitesides, R; You, X; Frenklach, M
2010-03-18
New simulations of graphene growth in flame environments are presented. The simulations employ a kinetic Monte Carlo (KMC) algorithm coupled to molecular mechanics (MM) geometry optimization to track individual graphenic species as they evolve. Focus is given to incorporation of five-member rings and resulting curvature and edge defects. The model code has been re-written to be more computationally efficient enabling a larger set of simulations to be run, decreasing stochastic fluctuations in the averaged results. The model also includes updated rate coefficients for graphene edge reactions recently published in the literature. The new simulations are compared to results from the previous model as well as to hydrogen to carbon ratios recorded in experiment and calculated with alternate models.
Cosmological Implications of the Uncertainty in Astrochemical Rate Coefficients
NASA Technical Reports Server (NTRS)
Glover, S. C. O.; Savin, D. W.; Jappsen, A.-K.
2006-01-01
The cooling of neutral gas of primordial composition, or with very low levels of metal enrichment, depends crucially on the formation of molecular coolants, such as H2 and HD within the gas. Although the chemical reactions involved in the formation and destruction of these molecules are well known, the same cannot be said for the rate coefficients of these reactions, some of which are uncertain by an order of magnitude. Here we discuss two reactions for which large uncertainties exist the formation of H2 by associative detachment of H- with H and the destruction of H- by mutual neutralization with protons. We show that these uncertainties can have a dramatic impact on the effectiveness of cooling during protogalactic collapse.
Absolute rate of the reaction of hydrogen atoms with ozone from 219-360 K
NASA Technical Reports Server (NTRS)
Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.
1978-01-01
Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence technique. The results can be expressed in Arrhenius form by K = (1.33 plus or minus 0.32)x10 to the minus 10 power exp (-449 plus or minus 58/T) cu cm/molecule/s (two standard deviations). The present work is compared to two previous determinations and is discussed theoretically.
Viggiano, Albert A; Friedman, Jeffrey F; Shuman, Nicholas S; Miller, Thomas M; Schaffer, Linda C; Troe, Jürgen
2010-05-21
Thermal electron attachment to C(60) has been studied by relative rate measurements in a flowing afterglow Langmuir probe apparatus. The rate coefficients of the attachment k(1) are shown to be close to 10(-6) cm(3) s(-1) with a small negative temperature coefficient. These results supersede measurements from the 1990s which led to much smaller values of k(1) with a large positive temperature coefficient suggesting an activation barrier. Theoretical modeling of k(1) in terms of generalized Vogt-Wannier capture theory shows that k(1) now looks more consistent with measurements of absolute attachment cross sections sigma(at) than before. The comparison of capture theory and experimental rate or cross section data leads to empirical correction factors, accounting for "intramolecular vibrational relaxation" or "electron-phonon coupling," which reduce k(1) below the capture results and which, on a partial wave-selected level, decrease with increasing electron energy. PMID:20499963
Photolysis Rate Coefficient Calculations in Support of SOLVE II
NASA Technical Reports Server (NTRS)
Swartz, William H.
2005-01-01
A quantitative understanding of photolysis rate coefficients (or "j-values") is essential to determining the photochemical reaction rates that define ozone loss and other crucial processes in the atmosphere. j-Values can be calculated with radiative transfer models, derived from actinic flux observations, or inferred from trace gas measurements. The primary objective of the present effort was the accurate calculation of j-values in the Arctic twilight along NASA DC-8 flight tracks during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II), based in Kiruna, Sweden (68 degrees N, 20 degrees E) during January-February 2003. The JHU/APL radiative transfer model was utilized to produce a large suite of j-values for photolysis processes (over 70 reactions) relevant to the upper troposphere and lower stratosphere. The calculations take into account the actual changes in ozone abundance and apparent albedo of clouds and the Earth surface along the aircraft flight tracks as observed by in situ and remote sensing platforms (e.g., EP-TOMS). A secondary objective was to analyze solar irradiance data from NCAR s Direct beam Irradiance Atmospheric Spectrometer (DIAS) on-board the NASA DC-8 and to start the development of a flexible, multi-species spectral fitting technique for the independent retrieval of O3,O2.02, and aerosol optical properties.
Absolute Density Calibration Cell for Laser Induced Fluorescence Erosion Rate Measurements
NASA Technical Reports Server (NTRS)
Domonkos, Matthew T.; Stevens, Richard E.
2001-01-01
Flight qualification of ion thrusters typically requires testing on the order of 10,000 hours. Extensive knowledge of wear mechanisms and rates is necessary to establish design confidence prior to long duration tests. Consequently, real-time erosion rate measurements offer the potential both to reduce development costs and to enhance knowledge of the dependency of component wear on operating conditions. Several previous studies have used laser-induced fluorescence (LIF) to measure real-time, in situ erosion rates of ion thruster accelerator grids. Those studies provided only relative measurements of the erosion rate. In the present investigation, a molybdenum tube was resistively heated such that the evaporation rate yielded densities within the tube on the order of those expected from accelerator grid erosion. This work examines the suitability of the density cell as an absolute calibration source for LIF measurements, and the intrinsic error was evaluated.
Proton Transfer Rate Coefficient Measurements of Selected Volatile Organic Molecules
NASA Astrophysics Data System (ADS)
Brooke, G.; Popović, S.; Vušković, L.
2002-05-01
We have developed an apparatus based on the selected ion flow tube (SIFT)footnote D. Smith and N.G. Adams, Ads. At. Mol. Phys. 24, 1 (1987). that allows the study of proton transfer between various positive ions and volatile organic molecules. Reactions in the flow tube occur at pressures of approximately 300 mTorr, eliminating the requirement of thermal beam production. The proton donor molecule H_3O^+ has been produced using several types of electrical discharges in water vapor, such as a capacitively coupled RF discharge and a DC hollow cathode discharge. Presently we are developing an Asmussen-type microwave cavity discharge using the components of a standard microwave oven that has the advantages of simple design and operation, as well as low cost. We will be presenting the results of the microwave cavity ion source to produce H_3O^+, and compare it to the other studied sources. In addition, we will be presenting a preliminary measurement of the proton transfer rate coefficient in the reaction of H_3O^+ with acetone and methanol.
Photolysis Rate Coefficient Calculations in Support of SOLVE Campaign
NASA Technical Reports Server (NTRS)
Lloyd, Steven A.; Swartz, William H.
2001-01-01
The objectives for this SOLVE project were 3-fold. First, we sought to calculate a complete set of photolysis rate coefficients (j-values) for the campaign along the ER-2 and DC-8 flight tracks. En route to this goal, it would be necessary to develop a comprehensive set of input geophysical conditions (e.g., ozone profiles), derived from various climatological, aircraft, and remotely sensed datasets, in order to model the radiative transfer of the atmosphere accurately. These j-values would then need validation by comparison with flux-derived j-value measurements. The second objective was to analyze chemistry along back trajectories using the NASA/Goddard chemistry trajectory model initialized with measurements of trace atmospheric constituents. This modeling effort would provide insight into the completeness of current measurements and the chemistry of Arctic wintertime ozone loss. Finally, we sought to coordinate stellar occultation measurements of ozone (and thus ozone loss) during SOLVE using the MSX/UVISI satellite instrument. Such measurements would determine ozone loss during the Arctic polar night and represent the first significant science application of space-based stellar occultation in the Earth's atmosphere.
Photolysis Rate Coefficient Calculations in Support of SOLVE Campaign
NASA Technical Reports Server (NTRS)
Lloyd, Steven A.; Swartz, William H.
2001-01-01
The objectives for this SOLVE project were 3-fold. First, we sought to calculate a complete set of photolysis rate coefficients (j-values) for the campaign along the ER-2 and DC-8 flight tracks. En route to this goal, it would be necessary to develop a comprehensive set of input geophysical conditions (e.g., ozone profiles), derived from various climatological, aircraft, and remotely sensed datasets, in order to model the radiative transfer of the atmosphere accurately. These j-values would then need validation by comparison with flux-derived j-value measurements. The second objective was to analyze chemistry along back trajectories using the NASA/Goddard chemistry trajectory model initialized with measurements of trace atmospheric constituents. This modeling effort would provide insight into the completeness of current measurements and the chemistry of Arctic wintertime ozone loss. Finally, we sought to coordinate stellar occultation measurements of ozone (and thus ozone loss) during SOLVE using the Midcourse Space Experiment(MSX)/Ultraviolet and Visible Imagers and Spectrographic Imagers (UVISI) satellite instrument. Such measurements would determine ozone loss during the Arctic polar night and represent the first significant science application of space-based stellar occultation in the Earth's atmosphere.
A Coefficient for Measuring the Agreement on Bipolar Rating Scales.
ERIC Educational Resources Information Center
Viernstein, Nikolaus
1990-01-01
A new coefficient--psi-star--is presented for measuring agreement on bidirectional response continua. The coefficient is designed to measure agreement in larger square contingency tables with even numbers of rows and columns. Advantages of the procedure are discussed. (SLD)
Rate coefficients for N2(+)(v) dissociative recombination
NASA Astrophysics Data System (ADS)
Bates, D. R.; Mitchell, J. B. A.
1991-09-01
The data of Zipf (1980) on N2(+)(v) dissociative recombination are analyzed taking into account the fact that there is coupling due to reversible symmetrical resonance charge transfer, N2(+)(v) + N2(0) yields N2(+)(0) + N2(v). The vibrational deactivation in N2(+)(v)-Ne collisions is also considered. A reported experimental value of the vibrational deactivation coefficient is found to be much higher than can be reconciled with the results of Zipf and it is therefore rejected. The analysis shows that the recombination coefficient for N2(+)(0) is about 2.6 x 10 exp-7 cu cm/s at 300 K and that recombination coefficients for N2(+)(1) and N2(+)(2) are substantially smaller. It is concluded that these coefficients conflict with the dissociative recombination cross section vs energy curve obtained by the merged beam method.
Absolute rate parameters for the reaction of atomic hydrogen with hydrazine
NASA Technical Reports Server (NTRS)
Stief, L. J.; Payne, W. A.
1976-01-01
Absolute rate parameters for the reaction of atomic hydrogen with hydrazine H + N2H4 yields H2 + N2H3 have been determined in a direct manner using flash photolysis of dilute mixtures of hydrazine in helium and time dependent observation of H via resonance fluorescence. By measuring the H-atom decay under pseudo-first-order conditions, the bimolecular rate constant K sub 1 was obtained over the temperature range 228-400 K. The data were fitted with good linearity to the Arrhenius expression K sub 1 = (9.87 plus or minus 1.17) x 10 to the -12th exp(-2380 plus or minus 100/RT) cu cm/molecule/s. The data were shown to be free of any contributions from secondary reactions involving H as a reactant or product.
Einstein A coefficients and absolute line intensities for the E2Π-X2Σ+ transition of CaH
NASA Astrophysics Data System (ADS)
Li, Gang; Harrison, Jeremy J.; Ram, Ram S.; Western, Colin M.; Bernath, Peter F.
2012-01-01
Einstein A coefficients and absolute line intensities have been calculated for the E2Π-X2Σ+ transition of CaH. Using wavefunctions derived from the Rydberg-Klein-Rees (RKR) method and electronic transition dipole moment functions obtained from high-level ab initio calculations, rotationless transition dipole moment matrix elements have been calculated for all 10 bands involving v‧=0,1 of the E2Π state and v″=0,1,2,3,4 of the X2Σ state. The rotational line strength factors (Hönl-London factors) are derived for the intermediate coupling case between Hund's case (a) and (b) for the E2Π-X2Σ+ transition. The computed transition dipole moments and the spectroscopic constants from a recent study [Ram et al., Journal of Molecular Spectroscopy 2011;266:86-91] have been combined to generate line lists containing Einstein A coefficients and absolute line intensities for 10 bands of the E2Π-X2Σ+ transition of CaH for J-values up to 50.5. The absolute line intensities have been used to determine a rotational temperature of 778±3 °C for the CaH sample in the recent study.
Rate Coefficient Determinations for H + NO2 → OH + NO from High Pressure Flow Reactor Measurements.
Haas, Francis M; Dryer, Frederick L
2015-07-16
Rate coefficients for the reaction H + NO2 → OH + NO (R1) have been determined over the nominal temperature and pressure ranges of 737-882 K and 10-20 atm, respectively, from measurements in two different flow reactor facilities: one laminar and one turbulent. Considering the existing database of experimental k1 measurements, the present conditions add measurements of k1 at previously unconsidered temperatures between ∼820-880 K, as well as at pressures that exceed existing measurements by over an order of magnitude. Experimental measurements of NOx-perturbed H2 oxidation have been interpreted by a quasi-steady state NOx plateau (QSSP) method. At the QSSP conditions considered here, overall reactivity is sensitive only to the rates of R1 and H + O2 + M → HO2 + M (R2.M). Consequently, the ratio of k1 to k2.M may be extracted as a simple algebraic function of measured NO2, O2, and total gas concentrations with only minimal complication (within measurement uncertainty) due to treatment of overall gas composition M that differs slightly from pure bath gas B. Absolute values of k1 have been determined with reference to the relatively well-known, pressure-dependent rate coefficients of R2.B for B = Ar and N2. Rate coefficients for the title reaction determined from present experimental interpretation of both laminar and turbulent flow reactor results appear to be in very good agreement around a representative value of 1.05 × 10(14) cm(3) mol(-1) s(-1) (1.74 × 10(-10) cm(3) molecule(-1) s(-1)). Further, the results of this study agree both with existing low pressure flash photolysis k1 determinations of Ko and Fontijn (J. Phys. Chem. 95 3984) near 760 K as well as a present fit to the theoretical expression of Su et al. (J. Phys. Chem. A 106 8261). These results indicate that, over the temperature range considered in this study and up to at least 20 atm, net chemistry due to stabilization of the H-NO2 reaction intermediate to form isomers of HNO2 may proceed at
Membrane electroporation: The absolute rate equation and nanosecond time scale pore creation
NASA Astrophysics Data System (ADS)
Vasilkoski, Zlatko; Esser, Axel T.; Gowrishankar, T. R.; Weaver, James C.
2006-08-01
The recent applications of nanosecond, megavolt-per-meter electric field pulses to biological systems show striking cellular and subcellular electric field induced effects and revive the interest in the biophysical mechanism of electroporation. We first show that the absolute rate theory, with experimentally based parameter input, is consistent with membrane pore creation on a nanosecond time scale. Secondly we use a Smoluchowski equation-based model to formulate a self-consistent theoretical approach. The analysis is carried out for a planar cell membrane patch exposed to a 10ns trapezoidal pulse with 1.5ns rise and fall times. Results demonstrate reversible supraelectroporation behavior in terms of transmembrane voltage, pore density, membrane conductance, fractional aqueous area, pore distribution, and average pore radius. We further motivate and justify the use of Krassowska’s asymptotic electroporation model for analyzing nanosecond pulses, showing that pore creation dominates the electrical response and that pore expansion is a negligible effect on this time scale.
EVAPOTRANSPIRATION RATES AND CROP COEFFICIENTS FOR LOWBUSH BLUEBERRY (Vaccinium angustifolium)
Technology Transfer Automated Retrieval System (TEKTRAN)
Lowbush blueberry (Vaccinium angustifolium) yield is strongly influenced by water availability; however, growers need more specific irrigation recommendations in order to optimize water use efficiency. Weighing lysimeters were used to determine actual evapotranspiration (ET) rates of lowbush bluebe...
Bénilan, Y; Bruston, P; Raulin, F; Courtin, R; Guillemin, J C
1995-01-01
The interpretation of mid-UV albedo spectra of planetary atmospheres, especially that of Titan, is the main goal of the SIPAT (Spectroscopie uv d'Interet Prebiologique dans l'Atmosphere de Titan) research program. This laboratory experiment has been developed in order to systematically determine the absorption coefficients of molecular compounds which are potential absorbers of scattered sunlight in planetary atmospheres, with high spectral resolution, and at various temperatures below room temperature. From photochemical modelling and experimental simulations, we may expect triacetylene (C6H2) to be present in the atmosphere of Titan, even though it has not yet been detected. We present here the first determination of the absolute absorption coefficient of that compound in the 200-300 nm range and at two temperatures (296 K and 233 K). The temperature dependence of the C6H2 absorption coefficient in that wavelength range is compared to that previously observed in the case of cyanoacetylene (HC3N). We then discuss the implications of the present results for the interpretation of Titan UV spectra, where it appears that large uncertainities can be introduced either by the presence of trace impurities in laboratory samples or by the variations of absorption coefficients with temperature. PMID:11538441
Temperature dependences of rate coefficients for electron catalyzed mutual neutralization
Shuman, Nicholas S.; Miller, Thomas M.; Friedman, Jeffrey F.; Viggiano, Albert A.; Maeda, Satoshi; Morokuma, Keiji
2011-07-14
The flowing afterglow technique of variable electron and neutral density attachment mass spectrometry (VENDAMS) has recently yielded evidence for a novel plasma charge loss process, electron catalyzed mutual neutralization (ECMN), i.e., A{sup +}+ B{sup -}+ e{sup -}{yields} A + B + e{sup -}. Here, rate constants for ECMN of two polyatomic species (POCl{sub 3}{sup -} and POCl{sub 2}{sup -}) and one diatomic species (Br{sub 2}{sup -}) each with two monatomic cations (Ar{sup +}and Kr{sup +}) are measured using VENDAMS over the temperature range 300 K-500 K. All rate constants show a steep negative temperature dependence, consistent with that expected for a three body process involving two ions and an electron. No variation in rate constants as a function of the cation type is observed outside of uncertainty; however, rate constants of the polyatomic anions ({approx}1 x 10{sup -18} cm{sup 6} s{sup -1} at 300 K) are measurably higher than that for Br{sub 2}{sup -}[(5.5 {+-} 2) x 10{sup -19} cm{sup 6} s{sup -1} at 300 K].
Refinement of the aeronomically determined rate coefficient for the reaction of N2/+/ with O
NASA Technical Reports Server (NTRS)
Torr, D. G.
1979-01-01
An earlier aeronomic determination of the rate coefficient for the reaction N2(+) + O yields NO(+) + N using Atmosphere Explorer data indicated a small increase in the rate coefficient with ion temperature, contrary to laboratory observations. This was incorrectly attributed to neglect of an increase in the N2(+) recombination rate with vibrational excitation. Recent aeronomical results have shown that the rate coefficient for charge exchange of O(+)(2D) with N2 is about an order of magnitude smaller at thermal temperatures than at energies greater than 0.5 eV (i.e., energies at which laboratory measurements have been made). It is shown that the use of the smaller charge exchange rate coefficient coupled with recent results on N2 quenching of O(+)(2D) yields a temperature dependence in excellent agreement with the laboratory results for the rate coefficient.
Subjective evaluation of HDTV stereoscopic videos in IPTV scenarios using absolute category rating
NASA Astrophysics Data System (ADS)
Wang, K.; Barkowsky, M.; Cousseau, R.; Brunnström, K.; Olsson, R.; Le Callet, P.; Sjöström, M.
2011-03-01
Broadcasting of high definition (HD) stereobased 3D (S3D) TV are planned, or has already begun, in Europe, the US, and Japan. Specific data processing operations such as compression and temporal and spatial resampling are commonly used tools for saving network bandwidth when IPTV is the distribution form, as this results in more efficient recording and transmission of 3DTV signals, however at the same time it inevitably brings quality degradations to the processed video. This paper investigated observers quality judgments of state of the art video coding schemes (simulcast H.264/AVC or H.264/MVC), with or without added temporal and spatial resolution reduction of S3D videos, by subjective experiments using the Absolute Category Rating method (ACR) method. The results showed that a certain spatial resolution reduction working together with high quality video compressing was the most bandwidth efficient way of processing video data when the required video quality is to be judged as "good" quality. As the subjective experiment was performed in two different laboratories in two different countries in parallel, a detailed analysis of the interlab differences was performed.
Coordinate-dependent diffusion coefficients: Decay rate in open quantum systems
Sargsyan, V. V.; Palchikov, Yu. V.; Antonenko, N. V.; Kanokov, Z.; Adamian, G. G.
2007-06-15
Based on a master equation for the reduced density matrix of an open quantum collective system, the influence of coordinate-dependent microscopical diffusion coefficients on the decay rate from a metastable state is treated. For various frictions and temperatures larger than a crossover temperature, the quasistationary decay rates obtained with the coordinate-dependent microscopical set of diffusion coefficients are compared with those obtained with the coordinate-independent microscopical set of diffusion coefficients and coordinate-independent and -dependent phenomenological sets of diffusion coefficients. Neglecting the coordinate dependence of diffusion coefficients, one can strongly overestimate or underestimate the decay rate at low temperature. The coordinate-dependent phenomenological diffusion coefficient in momentum are shown to be suitable for applications.
Hessler, J.P.; Ogren, P.J.
1992-08-31
A technique was developed for determining relative importance and correlation between reactions making up a complex kinetic system. This technique was used to investigate measurements of optical absorption cross sections and the correlation between cross sections and measured rate coefficients. It is concluded that (1) species, initial conditions, and temporal regions may be identified where cross sections may be measured without interference from the kinetic behavior of the observed species and (2) experiments designed to measure rate coefficients will always be correlated with the absorption cross section of the observed species. This correlation may reduce the accuracy of rate coefficient measurements.
NASA Astrophysics Data System (ADS)
Nielsen, Lars; Hansen, Jens Morten; Hede, Mikkel Ulfeldt; Clemmensen, Lars B.; Pejrup, Morten; Noe-Nygaard, Nanna
2014-11-01
Relative sea level curves contain coupled information about absolute sea level change and vertical lithospheric movement. Such curves may be constructed based on, for example tide gauge data for the most recent times and different types of geological data for ancient times. Correct account for vertical lithospheric movement is essential for estimation of reliable values of absolute sea level change from relative sea level data and vise versa. For modern times, estimates of vertical lithospheric movement may be constrained by data (e.g. GPS-based measurements), which are independent from the relative sea level data. Similar independent data do not exist for ancient times. The purpose of this study is to test two simple inversion approaches for simultaneous estimation of lithospheric uplift rates and absolute sea level change rates for ancient times in areas where a dense coverage of relative sea level data exists and well-constrained average lithospheric movement values are known from, for example glacial isostatic adjustment (GIA) models. The inversion approaches are tested and used for simultaneous estimation of lithospheric uplift rates and absolute sea level change rates in southwest Scandinavia from modern relative sea level data series that cover the period from 1900 to 2000. In both approaches, a priori information is required to solve the inverse problem. A priori information about the average vertical lithospheric movement in the area of interest is critical for the quality of the obtained results. The two tested inversion schemes result in estimated absolute sea level rise of ˜1.2/1.3 mm yr-1 and vertical uplift rates ranging from approximately -1.4/-1.2 mm yr-1 (subsidence) to about 5.0/5.2 mm yr-1 if an a priori value of 1 mm yr-1 is used for the vertical lithospheric movement throughout the study area. In case the studied time interval is broken into two time intervals (before and after 1970), absolute sea level rise values of ˜0.8/1.2 mm yr-1 (before
Rate Coefficient Measurements of the Reaction CH3 + O2 = CH3O + O
NASA Technical Reports Server (NTRS)
Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.
1999-01-01
Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, sub -0.47 ) x 10(exp 13) e(-15813 +/- 587 K/T)/cubic cm.mol.s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.
Rate Coefficient Measurements of the Reaction CH3+O2+CH3O+O
NASA Technical Reports Server (NTRS)
Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.
1999-01-01
Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, -0.47)) X 10(exp 13) exp(- 15813 +/- 587 K/T)cc/mol s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.
Rate Coefficients for the OH + (CHO)2 (Glyoxal) Reaction Between 240 and 400 K
NASA Astrophysics Data System (ADS)
Feierabend, K. J.; Talukdar, R. K.; Zhu, L.; Ravishankara, A. R.; Burkholder, J. B.
2006-12-01
Glyoxal (CHO)2, the simplest dialdehyde, is an end product formed in the atmospheric oxidation of biogenic hydrocarbons, for example, isoprene. As such, glyoxal plays a role in regional air quality and ozone production in certain locations. Glyoxal is lost in the atmosphere via UV photolysis and reaction with OH. However, the currently available rate coefficient data for the OH + glyoxal reaction is limited to a single room- temperature measurement made using the relative rate method. A determination of the rate coefficient temperature dependence is therefore needed for a more complete interpretation of the atmospheric processing of glyoxal. This study reports the rate coefficient for the OH + (CHO)2 reaction measured under pseudo- first-order conditions in OH ([(CHO)2] > 1000 [OH]0). OH radicals were produced using 248 nm pulsed laser photolysis of H2O2 or HNO3 and detected by pulsed laser induced fluorescence. The concentration of glyoxal in the reactor was determined using three independent techniques; gas flow rates as well as in situ UV and IR absorption. The total pressure in the reactor was varied from 40 to 300 Torr (He), and the rate coefficient was found to be independent of pressure over the temperature range studied. The rate coefficient exhibits a negative temperature dependence between 240 and 400 K consistent with the dependence previously observed for many other aldehydes. Our room-temperature rate coefficient is smaller than the relative rate value that is currently recommended for use in atmospheric model calculations. Our measured rate coefficients are discussed with respect to those for other aldehydes. The atmospheric implications of our work will also be discussed.
NASA Astrophysics Data System (ADS)
Wojnárovits, László; Takács, Erzsébet
2014-03-01
Rate coefficients published in the literature on hydroxyl radical reactions with pesticides and related compounds are discussed together with the experimental methods and the basic reaction mechanisms. Recommendations are made for the most probable values. Most of the molecules whose rate coefficients are discussed have aromatic ring: their rate coefficients are in the range of 2×109-1×1010 mol-1 dm3 s-1. The rate coefficients show some variation with the electron withdrawing-donating nature of the substituent on the ring. The rate coefficients for triazine pesticides (simazine, atrazine, prometon) are all around 2.5×109 mol-1 dm3 s-1. The values do not show variation with the substituent on the s-triazine ring. The rate coefficients for the non-aromatic molecules which have C=C double bonds or several C-H bonds may also be above 1×109 mol-1 dm3 s-1. However, the values for molecules without C=C double bonds or several C-H bonds are in the 1×107-1×109 mol-1 dm3 s-1 range.
HTO washout model: on the relationship between exchange rate and washout coefficient
Golubev, A.; Balashov, Y.; Mavrin, S.; Golubeva, V.; Galeriu, D.
2015-03-15
Washout coefficient Λ is widely used as a parameter in washout models. These models describes overall HTO washout with rain by a first-order kinetic equation, while washout coefficient Λ depends on the type of rain event and rain intensity and empirical parameters a, b. The washout coefficient is a macroscopic parameter and we have considered in this paper its relationship with a microscopic rate K of HTO isotopic exchange in atmospheric humidity and drops of rainwater. We have shown that the empirical parameters a, b can be represented through the rain event characteristics using the relationships of molecular impact rate, rain intensity and specific rain water content while washout coefficient Λ can be represented through the exchange rate K, rain intensity, raindrop diameter and terminal raindrop velocity.
Muramatsu, Chisako; Li Qiang; Schmidt, Robert A.; Shiraishi, Junji; Suzuki, Kenji; Newstead, Gillian M.; Doi, Kunio
2007-07-15
The presentation of images that are similar to that of an unknown lesion seen on a mammogram may be helpful for radiologists to correctly diagnose that lesion. For similar images to be useful, they must be quite similar from the radiologists' point of view. We have been trying to quantify the radiologists' impression of similarity for pairs of lesions and to establish a ''gold standard'' for development and evaluation of a computerized scheme for selecting such similar images. However, it is considered difficult to reliably and accurately determine similarity ratings, because they are subjective. In this study, we compared the subjective similarities obtained by two different methods, an absolute rating method and a 2-alternative forced-choice (2AFC) method, to demonstrate that reliable similarity ratings can be determined by the responses of a group of radiologists. The absolute similarity ratings were previously obtained for pairs of masses and pairs of microcalcifications from five and nine radiologists, respectively. In this study, similarity ranking scores for eight pairs of masses and eight pairs of microcalcifications were determined by use of the 2AFC method. In the first session, the eight pairs of masses and eight pairs of microcalcifications were grouped and compared separately for determining the similarity ranking scores. In the second session, another similarity ranking score was determined by use of mixed pairs, i.e., by comparison of the similarity of a mass pair with that of a calcification pair. Four pairs of masses and four pairs of microcalcifications were grouped together to create two sets of eight pairs. The average absolute similarity ratings and the average similarity ranking scores showed very good correlations in the first study (Pearson's correlation coefficients: 0.94 and 0.98 for masses and microcalcifications, respectively). Moreover, in the second study, the correlations between the absolute ratings and the ranking scores were also
NASA Astrophysics Data System (ADS)
Song, L.; Balakrishnan, N.; Walker, K. M.; Stancil, P. C.; Thi, W. F.; Kamp, I.; van der Avoird, A.; Groenenboom, G. C.
2015-11-01
We present calculated rate coefficients for ro-vibrational transitions of CO in collisions with H atoms for a gas temperature range of 10 K ≤ T ≤ 3000 K, based on the recent three-dimensional ab initio H-CO interaction potential of Song et al. Rate coefficients for ro-vibrational v=1,j=0-30\\to v\\prime =0,j\\prime transitions were obtained from scattering cross sections previously computed with the close-coupling (CC) method by Song et al. Combining these with the rate coefficients for vibrational v=1-5\\to v\\prime \\lt v quenching obtained with the infinite-order sudden approximation, we propose a new extrapolation scheme that yields the rate coefficients for ro-vibrational v=2-5,j=0-30\\to v\\prime ,j\\prime de-excitation. Cross sections and rate coefficients for ro-vibrational v=2,j=0-30\\to v\\prime =1,j\\prime transitions calculated with the CC method confirm the effectiveness of this extrapolation scheme. Our calculated and extrapolated rates are very different from those that have been adopted in the modeling of many astrophysical environments. The current work provides the most comprehensive and accurate set of ro-vibrational de-excitation rate coefficients for the astrophysical modeling of the H-CO collision system. The application of the previously available and new data sets in astrophysical slab models shows that the line fluxes typically change by 20%-70% in high temperature environments (800 K) with an H/H2 ratio of 1; larger changes occur for lower temperatures.
NASA Technical Reports Server (NTRS)
Keyser, L. F.
1980-01-01
The absolute rate constant of the reaction between chlorine (2P) atoms and hydrogen peroxide was determined from 298 to 424 K, using the discharge flow resonance fluorescence technique. Pseudo-first-order conditions were used with hydrogen peroxide in large excess. A fast flow-sampling procedure limited hydrogen peroxide decomposition to less than 5% over the temperature range studied. At 298 K, the rate constant is (4.1 plus or minus 0.2) x 10 to the minus 13th cu cm/molecule-sec.
Neufeld, David A.
2010-01-01
An artificial neural network (ANN) is investigated as a tool for estimating rate coefficients for the collisional excitation of molecules. The performance of such a tool can be evaluated by testing it on a data set of collisionally induced transitions for which rate coefficients are already known: the network is trained on a subset of that data set and tested on the remainder. Results obtained by this method are typically accurate to within a factor of approx2.1 (median value) for transitions with low excitation rates and approx1.7 for those with medium or high excitation rates, although 4% of the ANN outputs are discrepant by a factor of 10 or more. The results suggest that ANNs will be valuable in extrapolating a data set of collisional rate coefficients to include high-lying transitions that have not yet been calculated. For the asymmetric top molecules considered in this paper, the favored architecture is a cascade-correlation network that creates 16 hidden neurons during the course of training, with three input neurons to characterize the nature of the transition and one output neuron to provide the logarithm of the rate coefficient.
NASA Astrophysics Data System (ADS)
Dransfield, T. J.; Gennaco, M. M.; Huang, Y.; Hannun, R. A.
2011-12-01
We report absolute measurements of the rate constants of the reaction of hydroxyl radical (OH) with cyclopentane and cycloheptane in 6-8 Torr of nitrogen from 230-350 K using Harvard's High Pressure Flow System. Ethane's reactivity was simultaneously measured as a test of experimental performance. Hydroxyl concentrations were measured using Laser-Induced Fluorescence, and alkane concentrations were measured using Fourier-Transform Infrared Spectroscopy. Recent work on this flow system has suggested that cyclohexane has a significantly higher activation energy to reaction with OH than does cyclo-octane, a result which is not suggested by our understanding of hydrocarbon reactivity nor predicted by structure-activity relationships. This work examines the temperature dependent rates for two other similarly-sized cycloalkanes to determine whether they behave as cyclohexane or as cyclooctane. While several previous experiments have studied the reaction with cyclopentane, there is significant scatter in the room temperature rates, and only four absolute rate measurements are available at non-ambient temperatures. There are only two absolute rate measurements available for the reaction with cycloheptane; only one of these reports a temperature dependence, and that study is limited to temperatures above 298 K. Thus, this work significantly expands the available data set for both reactions. The data for the reactions of OH with ethane, cyclopentane, cyclohexane, and cycloheptane are all modeled using a simple Arrhenius fit, and also with a modified Arrhenius equation based on transition state theory, ignoring tunneling. Results from the latter fit indicate that the activation barriers for both title reactions are greater than that of OH + cyclo-octane. The measured activation energy for OH + cyclopentane actually exceeds that of OH + cyclohexane.
Kinetic models for coagulation processes: determination of rate coefficients in vivo
NASA Astrophysics Data System (ADS)
Pearce, John A.; Cheong, Wai-Fung; Pandit, Kirit; McMurray, Tom J.; Thomsen, Sharon L.
1991-06-01
Kinetic models of thermal damage in tissues can be used to describe histologic end points obtained with laser irradiation. In this study, thermographic measurements of skin surface temperature distributions during laser impingement were used to derive a temperature history for the lesion site. Lesions were evaluated at 48 h after laser irradiation to determine the radius of purpura formation. The temperature histories at the maximum radius of purpura formation (threshold temperatures) were analyzed and plotted on Arrhenius axes to estimate rate coefficients for the process. As expected, transient in vivo thermal history data yielded a noisy Arrhenius plot; however, estimates of the appropriate rate coefficients for purpura formation in vivo could be made.
Easy Absolute Values? Absolutely
ERIC Educational Resources Information Center
Taylor, Sharon E.; Mittag, Kathleen Cage
2015-01-01
The authors teach a problem-solving course for preservice middle-grades education majors that includes concepts dealing with absolute-value computations, equations, and inequalities. Many of these students like mathematics and plan to teach it, so they are adept at symbolic manipulations. Getting them to think differently about a concept that they…
Global rate coefficients for ionization and recombination of carbon, nitrogen, oxygen, and argon
Annaloro, Julien; Morel, Vincent; Bultel, Arnaud; Omaly, Pierre
2012-07-15
The flow field modeling of planetary entry plasmas, laser-induced plasmas, inductively coupled plasmas, arcjets, etc., requires to use Navier-Stokes codes. The kinetic mechanisms implemented in these codes involve global (effective) rate coefficients. These rate coefficients result from the excited states coupling during a quasi-steady state. In order to obtain these global rate coefficients over a wide electron temperature (T{sub e}) range for ionization and recombination of carbon, nitrogen, oxygen, and argon, the behavior of their excited states is investigated using a zero-dimensional (time-dependent) code. The population number densities of these electronic states are considered as independent species. Their relaxation is studied within the range 3000 K{<=}T{sub e}{<=}20 000 K and leads to the determination of the ionization (k{sub i}) and recombination (k{sub r}) global rate coefficients. Comparisons with existing data are performed. Finally, the ratio k{sub i}/k{sub r} is compared with the Saha equilibrium constant. This ratio increases more rapidly than the equilibrium constant for T{sub e}>15 000 K.
Partial and total dielectronic recombination rate coefficients for W73+ to W56+
NASA Astrophysics Data System (ADS)
Preval, S. P.; Badnell, N. R.; O'Mullane, M. G.
2016-04-01
Dielectronic recombination (DR) is a key atomic process that affects the spectroscopic diagnostic modeling of tungsten, most of whose ionization stages will be found somewhere in the ITER fusion reactor: in the edge, divertor, or core plasma. Accurate DR data are sparse while complete DR coverage is unsophisticated (e.g., average-atom or Burgess General Formula), as illustrated by the large uncertainties that currently exist in the tungsten ionization balance. To this end, we present a series of partial final-state-resolved and total DR rate coefficients for W73+ to W56+ tungsten ions. This is part of a wider effort within The Tungsten Project to calculate accurate dielectronic recombination rate coefficients for the tungsten isonuclear sequence for use in collisional-radiative modeling of finite-density tokamak plasmas. The recombination rate coefficients have been calculated with autostructure using κ -averaged relativistic wave unctions in level resolution (intermediate coupling) and configuration resolution (configuration average). Comparison with previous calculations of total DR rate coefficients for W63+ and W56+ yield agreement to within 20% and 10%, respectively, at peak temperature. It is also seen that the Jüttner correction to the Maxwell distribution has a significant effect on the ionization balance of tungsten at the highest charge states, changing both the peak abundance temperatures and the ionization fractions of several ions.
Alman, D.A.; Brooks, J.N.; Ruzic, D.N.; Wang, Z.
1999-07-21
We estimate cross sections and rate coefficients for proton and electron impact ionization, dissociation, and recombination of neutral and ionized hydrocarbon molecules and fragments of the form C{sub x}H{sub y}{sup k}, x = 1-3, y = 1-6, k = 0,1 in a thermalized hydrogen-electron plasma.
NASA Technical Reports Server (NTRS)
Mickens, R. E.
1978-01-01
Two theorems based on Laplace transforms are used to relate threshold and high energy behavior to a temperature dependent variable. A recombination reaction involving electrically neutral species is presented to illustrate the dynamics of the activation energy and the associated rate coefficient. The distribution functions are shown to correspond with those predicted by Boltzmann's equations.
Camper, Anne K.; Hayes, Jason T.; Sturman, Paul J.; Jones, Warren L.; Cunningham, Alfred B.
1993-01-01
Three strains of Pseudomonas fluorescens with different motility rates and adsorption rate coefficients were injected into porous-medium reactors packed with l-mm-diameter glass spheres. Cell breakthrough, time to peak concentration, tailing, and cell recovery were measured at three interstitial pore velocities (higher than, lower than, and much lower than the maximal bacterial motility rate). All experiments were done with distilled water to reduce the effects of growth and chemotaxis. Contrary to expectations, motility did not result in either early breakthrough or early time to peak concentration at flow velocities below the motility rate. Bacterial size exclusion effects were shown to affect breakthrough curve shape at the very low flow velocity, but no such effect was seen at the higher flow velocity. The tendency of bacteria to adsorb to porous-medium surfaces, as measured by adsorption rate coefficients, profoundly influenced transport characteristics. Cell recoveries were shown to be correlated with the ratio of advective to adsorptive transport in the reactors. Adsorption rate coefficients were found to be better predictors of microbial transport phenomena than individual characteristics, such as size, motility, or porous-medium hydrodynamics. PMID:16349075
Detecting absolute human knee angle and angular velocity using accelerometers and rate gyroscopes.
Williamson, R; Andrews, B J
2001-05-01
Knee joint angle and angular velocity were calculated in real time during standing up and sitting down. Two small modules comprising rate gyroscopes and accelerometers were attached to the thigh and shank of two able-bodied volunteers and one T5 ASIA(A) paraplegic assisted by functional electrical stimulation (FES). The offset and drift of the rate gyroscopes was compensated for by auto-resetting and auto-nulling algorithms. The tilt of the limb segments was calculated by combining the signals of the accelerometer and the rate gyroscope. The joint angle was calculated as the difference in tilt of the segments. The modules were also tested on a two-dimensional model. The mean differences between the rate gyroscope-accelerometer system and the reference goniometer for the model, able-bodied and paraplegic standing trials were 2.1 degrees, 2.4 degrees and 2.3 degrees respectively for knee angle and 2.3 degrees s(-1), 5.0 degrees s(-1) and 11.8 degrees s(-1) respectively for knee velocity. The rate gyroscope-accelerometer system was more accurate than using the accelerometer as a tilt meter, possibly due to the greater bandwidth of the rate gyroscope-accelerometer system. PMID:11465883
Gurley, Katelyn; Shang, Yu; Yu, Guoqiang
2012-07-01
This study investigates a method using novel hybrid diffuse optical spectroscopies [near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS)] to obtain continuous, noninvasive measurement of absolute blood flow (BF), blood oxygenation, and oxygen consumption rate (V̇O(2)) in exercising skeletal muscle. Healthy subjects (n=9) performed a handgrip exercise to increase BF and V̇O(2) in forearm flexor muscles, while a hybrid optical probe on the skin surface directly monitored oxy-, deoxy-, and total hemoglobin concentrations ([HbO(2)], [Hb], and THC), tissue oxygen saturation (S(t)O(2)), relative BF (rBF), and relative oxygen consumption rate (rV̇O(2)). The rBF and rV̇O(2) signals were calibrated with absolute baseline BF and V̇O(2) obtained through venous and arterial occlusions, respectively. Known problems with muscle-fiber motion artifacts in optical measurements during exercise were mitigated using a novel gating algorithm that determined muscle contraction status based on control signals from a dynamometer. Results were consistent with previous findings in the literature. This study supports the application of NIRS/DCS technology to quantitatively evaluate hemodynamic and metabolic parameters in exercising skeletal muscle and holds promise for improving diagnosis and treatment evaluation for patients suffering from diseases affecting skeletal muscle and advancing fundamental understanding of muscle and exercise physiology. PMID:22894482
Gurley, Katelyn; Shang, Yu
2012-01-01
Abstract. This study investigates a method using novel hybrid diffuse optical spectroscopies [near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS)] to obtain continuous, noninvasive measurement of absolute blood flow (BF), blood oxygenation, and oxygen consumption rate (V˙O2) in exercising skeletal muscle. Healthy subjects (n=9) performed a handgrip exercise to increase BF and V˙O2 in forearm flexor muscles, while a hybrid optical probe on the skin surface directly monitored oxy-, deoxy-, and total hemoglobin concentrations ([HbO2], [Hb], and THC), tissue oxygen saturation (StO2), relative BF (rBF), and relative oxygen consumption rate (rV˙O2). The rBF and rV˙O2 signals were calibrated with absolute baseline BF and V˙O2 obtained through venous and arterial occlusions, respectively. Known problems with muscle-fiber motion artifacts in optical measurements during exercise were mitigated using a novel gating algorithm that determined muscle contraction status based on control signals from a dynamometer. Results were consistent with previous findings in the literature. This study supports the application of NIRS/DCS technology to quantitatively evaluate hemodynamic and metabolic parameters in exercising skeletal muscle and holds promise for improving diagnosis and treatment evaluation for patients suffering from diseases affecting skeletal muscle and advancing fundamental understanding of muscle and exercise physiology. PMID:22894482
NASA Astrophysics Data System (ADS)
Gurley, Katelyn; Shang, Yu; Yu, Guoqiang
2012-07-01
This study investigates a method using novel hybrid diffuse optical spectroscopies [near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS)] to obtain continuous, noninvasive measurement of absolute blood flow (BF), blood oxygenation, and oxygen consumption rate (\\Vdot O2) in exercising skeletal muscle. Healthy subjects (n=9) performed a handgrip exercise to increase BF and \\Vdot O2 in forearm flexor muscles, while a hybrid optical probe on the skin surface directly monitored oxy-, deoxy-, and total hemoglobin concentrations ([HbO2], [Hb], and THC), tissue oxygen saturation (StO2), relative BF (rBF), and relative oxygen consumption rate (r\\Vdot O2). The rBF and r\\Vdot O2 signals were calibrated with absolute baseline BF and \\Vdot O2 obtained through venous and arterial occlusions, respectively. Known problems with muscle-fiber motion artifacts in optical measurements during exercise were mitigated using a novel gating algorithm that determined muscle contraction status based on control signals from a dynamometer. Results were consistent with previous findings in the literature. This study supports the application of NIRS/DCS technology to quantitatively evaluate hemodynamic and metabolic parameters in exercising skeletal muscle and holds promise for improving diagnosis and treatment evaluation for patients suffering from diseases affecting skeletal muscle and advancing fundamental understanding of muscle and exercise physiology.
Measurement of 129Xe -Cs binary spin-exchange rate coefficient
NASA Astrophysics Data System (ADS)
Jau, Yuan-Yu; Kuzma, Nicholas N.; Happer, William
2004-06-01
We report the first measurement of the spin-exchange rate coefficient for binary collisions between Cs and 129Xe atoms in the temperature range 110
Unified Electron-Ion Recombination Rate Coefficients of Silicon and Sulfur Ions
NASA Astrophysics Data System (ADS)
Nahar, Sultana N.; Pradhan, Anil K.
1995-07-01
Total recombination rate coefficients for the astrophysically important Si and S ions, Si I, Si II, Si IX, S II, and S III, are obtained employing a new unified treatment developed for electron-ion recombination. The treatment incorporates both the radiative and the dielectronic recombination processes in the close coupling approximation from atomic collision theory, and the calculations are carried out using the R-matrix method as developed for the Opacity Project. All recombined states from the ground state to n = ∞ are considered. The states are divided into two groups, a low-n and a high-n group. Detailed partial photoionization cross sections into the ground state of the recombining ion, including autoionizing resonances due to coupling to excited states of the ion, are calculated for all bound states in the low-n group, and the Milne relation is used to calculate the corresponding contribution to the recombination rate coefficient. For the high-n group, collision strengths for dielectronic recombination, both detailed and resonance averaged, are obtained using the precise theory of Bell & Seaton. Total recombination rate coefficients are computed over a wide range of temperatures for practical purposes. A discussion of the atomic effects that determine the accuracy of the recombination rates is presented, in particular as a function of the increase in the eigenfunction expansion for the recombining ion, studied for e + Si X → Si IX. Comparison is made with earlier works.
Zilio, Valery Olivier; Joneja, Om Parkash; Popowski, Youri; Rosenfeld, Anatoly; Chawla, Rakesh
2006-06-15
Reported MOSFET measurements concern mostly external radiotherapy and in vivo dosimetry. In this paper, we apply the technique for absolute dosimetry in the context of HDR brachytherapy using an {sup 192}Ir source. Measured radial dose rate distributions in water for different planes perpendicular to the source axis are presented and special attention is paid to the calibration of the R and K type detectors, and to the determination of appropriate correction factors for the sensitivity variation with the increase of the threshold voltage and the energy dependence. The experimental results are compared with Monte Carlo simulated dose rate distributions. The experimental results show a good agreement with the Monte Carlo simulations: the discrepancy between experimental and Monte Carlo results being within 5% for 82% of the points and within 10% for 95% of the points. Moreover, all points except two are found to lie within the experimental uncertainties, confirming thereby the quality of the results obtained.
Transitions in genetic toggle switches driven by dynamic disorder in rate coefficients
NASA Astrophysics Data System (ADS)
Chen, Hang; Thill, Peter; Cao, Jianshu
2016-05-01
In biochemical systems, intrinsic noise may drive the system switch from one stable state to another. We investigate how kinetic switching between stable states in a bistable network is influenced by dynamic disorder, i.e., fluctuations in the rate coefficients. Using the geometric minimum action method, we first investigate the optimal transition paths and the corresponding minimum actions based on a genetic toggle switch model in which reaction coefficients draw from a discrete probability distribution. For the continuous probability distribution of the rate coefficient, we then consider two models of dynamic disorder in which reaction coefficients undergo different stochastic processes with the same stationary distribution. In one, the kinetic parameters follow a discrete Markov process and in the other they follow continuous Langevin dynamics. We find that regulation of the parameters modulating the dynamic disorder, as has been demonstrated to occur through allosteric control in bistable networks in the immune system, can be crucial in shaping the statistics of optimal transition paths, transition probabilities, and the stationary probability distribution of the network.
Transitions in genetic toggle switches driven by dynamic disorder in rate coefficients.
Chen, Hang; Thill, Peter; Cao, Jianshu
2016-05-01
In biochemical systems, intrinsic noise may drive the system switch from one stable state to another. We investigate how kinetic switching between stable states in a bistable network is influenced by dynamic disorder, i.e., fluctuations in the rate coefficients. Using the geometric minimum action method, we first investigate the optimal transition paths and the corresponding minimum actions based on a genetic toggle switch model in which reaction coefficients draw from a discrete probability distribution. For the continuous probability distribution of the rate coefficient, we then consider two models of dynamic disorder in which reaction coefficients undergo different stochastic processes with the same stationary distribution. In one, the kinetic parameters follow a discrete Markov process and in the other they follow continuous Langevin dynamics. We find that regulation of the parameters modulating the dynamic disorder, as has been demonstrated to occur through allosteric control in bistable networks in the immune system, can be crucial in shaping the statistics of optimal transition paths, transition probabilities, and the stationary probability distribution of the network. PMID:27155656
Absolute rate constant for the O plus NO chemiluminescence in the near infrared
NASA Technical Reports Server (NTRS)
Golde, M. F.; Roche, A. E.; Kaufman, F.
1973-01-01
Infrared chemiluminescence from the process O + NO (+M) NO2 + hv (+M) has been studied between 1.3 and 4.1 micrometer. The wavelength dependence of the continuum between 1.3 and 3.3 micrometer is in fair agreement with previous studies and the measured radiative rate constant at 1.51 micrometer establishes the NO-O glow in this spectral range as a secondary emission standard. Comparison with previous studies of the visible region of the glow implies that the overall radiative rate constant lies in the range (9.4 to 11.2) x 10 to the minus 17 power cu cm sec/1. In the region 3.3 to 4.1 micrometer, the previously observed broad band, peaking at 3.7 micrometer, shows a complex kinetic dependence on O and M.
Absolute rate of the reaction of bromine atoms with ozone from 200-360 K
NASA Technical Reports Server (NTRS)
Michael, J. V.; Lee, J. H.; Payne, W. A.; Stief, L. J.
1978-01-01
The rate constant for the reaction Br + O3 yields BrO + O2 was measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at lambda 165nm.O3 was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3, total pressure and limited variations in flash intensity. The measured rate constants obeyed the Arrhenius expression, where the error quoted is two standard deviations. Results are compared with previous determinations which employed the discharge flow-mass spectrometric technique.
Absolute rate constants for the reaction of atomic hydrogen with ketene from 298 to 500 K
NASA Technical Reports Server (NTRS)
Michael, J. V.; Nava, D. F.; Payne, W. A.; Stief, L. J.
1979-01-01
Rate constants for the reaction of atomic hydrogen with ketene have been measured at room temperature by two techniques, flash photolysis-resonance fluorescence and discharge flow-resonance fluorescence. The measured values are (6.19 + or - 1.68) x 10 to the -14th and (7.3 + or - 1.3) x 10 to the -14th cu cm/molecule/s, respectively. In addition, rate constants as a function of temperature have been measured over the range 298-500 K using the FP-RF technique. The results are best represented by the Arrhenius expression k = (1.88 + or - 1.12) x 10 to the -11th exp(-1725 + or - 190/T) cu cm/molecule/s, where the indicated errors are at the two standard deviation level.
Absolute rate of the reaction of bromine atoms with ozone from 200 to 360 K
NASA Technical Reports Server (NTRS)
Michael, J. V.; Lee, J. H.; Payne, W. A.; Stief, L. J.
1978-01-01
The rate constant for the reaction Br + O3 yields BrO + O2 has been measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at a wavelength of 165 nm. O3 concentration was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3 concentration, total pressure (Ar), and limited variations in flash intensity (i.e., initial Br concentration). The measured rate constants obey the Arrhenius expression, k = (7.74 plus or minus 0.50) x 10 to the -12th exp(-603 plus or minus 16/T) cu cm/molecule/sec, where the error quoted is two standard deviations.
Radiative rates and electron impact excitation rate coefficients for Ne-like selenium, Se XXV
Wang, K.; Chen, C.Y. Huang, M.; Wang, Y.S.; Zou, Y.M.
2011-07-15
In this article we report calculations of energy levels, radiative rates, electron impact collision strengths, and effective collision strengths for transitions among the 241 fine-structure levels arising from 2l{sup 8} and 2l{sup 7}n{sup '}l{sup '} (n{sup '{<=}}6 and l{sup '{<=}}n{sup '}-1) configurations of Ne-like Se XXV using the Flexible Atomic Code. Energy levels and radiative rates are calculated within the relativistic configuration-interaction method. Direct excitation collision strengths are calculated using the relativistic distorted-wave approximation and high-energy collision strengths are obtained in the relativistic plane-wave approximation. Resonance contributions through the relevant Na-like doubly-excited configurations 2l{sup 7}n'l'n''l'' (3{<=}n'{<=}7, l'{<=}n'-1, n'{<=}n''{<=}50, and l''{<=}8) are explicitly taken into account via the independent-process and isolated-resonance approximation using distorted waves. Resonant stabilizing transitions and possibly important radiative decays from the resonances toward low-lying autoionizing levels are considered. In addition, the resonance contributions from Na-like 2l{sup 6}3l'3l'''n''' (n'''=3-6) configurations are included and found to be predominant for many transitions among the singly-excited states in Ne-like Se XXV. We present the radiative rates, oscillator strengths, and line strengths for all electric dipole, magnetic dipole, electric quadrupole, magnetic quadrupole, electric octopole, and magnetic octopole transitions among the 241 levels. The effective collision strengths are reported for all 28920 transitions among the 241 levels over a wide temperature range up to 10 keV. To assess the reliability and accuracy of the present collisional data, we have performed a 27-state close-coupling calculation, employing the Dirac R-matrix theory. The results from the close-coupling calculation and the independent-process calculation for the identical target states are found to be in good agreement
Friction coefficients and wear rates of different orthodontic archwires in artificial saliva.
Alfonso, M V; Espinar, E; Llamas, J M; Rupérez, E; Manero, J M; Barrera, J M; Solano, E; Gil, F J
2013-05-01
The aim of this paper is to analyze the influence of the nature of the orthodontic archwires on the friction coefficient and wear rate against materials used commonly as brackets (Ti-6Al-4V and 316L Stainless Steel). The materials selected as orthodontic archwires were ASI304 stainless steel, NiTi, Ti, TiMo and NiTiCu. The array archwire's materials selected presented very similar roughness but different hardness. Materials were chosen from lower and higher hardness degrees than that of the brackets. Wear tests were carried out at in artificial saliva at 37 °C. Results show a linear relationship between the hardness of the materials and the friction coefficients. The material that showed lower wear rate was the ASI304 stainless steel. To prevent wear, the wire and the brackets have high hardness values and in the same order of magnitude. PMID:23440428
Electron-impact excitation rate-coefficients and polarization of subsequent emission for Ar+ ion
NASA Astrophysics Data System (ADS)
Dipti; Srivastava, Rajesh
2016-06-01
Electron impact excitation in Ar+ ions has been studied by using fully relativistic distorted wave theory. Calculations are performed to obtain the excitation cross-sections and rate-coefficients for the transitions from the ground state 3p5 (J=3/2) to fine-structure levels of excited states 3p44s, 3p44p, 3p45s, 3p45p, 3p43d and 3p44d. Polarization of the radiation following the excitation has been calculated using the obtained magnetic sub-level cross-sections. Comparison of the present rate-coefficients is also done with the previously reported theoretical results for some unresolved fine structure transitions.
Recommended Thermal Rate Coefficients for the C + H3+ Reaction and Some Astrochemical Implications
NASA Astrophysics Data System (ADS)
Vissapragada, Shreyas; Buzard, Cam; Miller, Kenneth A.; O'Connor, Aodh; De Ruette, Nathalie; Urbain, Xavier; Savin, Daniel Wolf
2016-06-01
We have incorporated our experimentally derived thermal rate coefficients for C + H3+ forming CH+ and CH2+ into a commonly used astrochemical model. We find that the Arrhenius-Kooij equation typically used in chemical models does not accurately fit our data and use instead a more versatile fitting formula. At a temperature of 10 K and a density of 104 cm-3, we find no significant differences in the predicted abundances, but at higher temperatures of 50, 100, and 300 K we find up to factor of 2 changes. Additionally, we find that the relatively small error on our measurements (~15%) significantly reduces the uncertainties on the predicted abundances compared to those obtained using the currently implemented Langevin rate coefficient with its estimated factor of 2 uncertainty.
Rate-coefficients and polarization results for the electron-impact excitation of Ar+ ion
NASA Astrophysics Data System (ADS)
Srivastava, Rajesh; Dipti, Dipti
2016-05-01
A fully relativistic distorted wave theory has been employed to study the electron impact excitation in Ar+ ion. Results have been obtained for the excitation cross-sections and rate-coefficients for the transitions from the ground state 3p5 (J = 3/2) to fine-structure levels of excited states 3p4 4 s, 3p4 4 p , 3p4 5 s, 3p4 5 p, 3p4 3 d and 3p4 4 d. Polarization of the radiation following the excitation has been calculated using the obtained magnetic sub-level cross-sections. Comparison of the present rate-coefficients is also done with the previously reported theoretical results for some unresolved fine structure transitions. Work is supported by DAE-BRNS Mumbai and CSIR, New Delhi.
NASA Astrophysics Data System (ADS)
Alba, S.; Weldon, R.; Livelybrooks, D.; Schmidt, D. A.
2009-12-01
We present a new uplift rate map for western Washington based on reanalysis of water levels from the 12 major NOAA tide gauges, three new water level series that combine NOAA’s historical records and our temporarily deployed gauges (at Cape Disappointment, Olympia, and Point Grenville), and reinterpretation of repeated 1st and 2nd order NGS leveling lines. As previous studies have concluded, EW gradients in the vertical deformation field are consistent with strain accumulation across the Cascadia subduction zone interface; however, uplift rates are highly variable along the outer Washington coast, ranging from approximately +4 to -2 mm/yr, suggesting significant changes in the depth of locking along strike. Improved measure of uplift rates from water level changes are accomplished by aggressively editing available hourly data and applying a transfer function approach to better remove tides, ocean and atmospheric “noise”. The analysis allows uplift to be determined from shorter and less complete records and in some cases permits the identification of transients like slow earthquakes. As we found in a similar study in Oregon (Burgette et al, JGR, 2009), releveled lines need to be anchored to as many tide gauges as possible to remove systematic error, and repeated releveling (especially of tidal benchmarks) is required to identify the few stable benchmarks that link water levels at the tidal stations to each other through time and to the regional NGS leveling lines. A portion of the westernmost Washington coast, from an approximate latitude of 47.4 to 47.9 N, is subsiding, and tilts suggest that the peak in uplift rate is well onshore, indicating that the locked zone extends onshore, in contrast to most previous studies. To the north, the peak in uplift approximately passes through Neah Bay (the NW corner of the Olympic Peninsula, lat. 48.3 N), and to the south the peak is offshore from Grays Harbor (lat. 47 N) to the Columbia River (lat. 46.2 N). A north
NASA Technical Reports Server (NTRS)
Lee, J. H.; Timmons, R. B.; Stief, L. J.
1976-01-01
It is pointed out that the investigated reaction of oxygen with dimethyl sulfide may play an important role in photochemical smog formation and in the chemical evolution of dense interstellar clouds. Kinetic data were obtained with the aid of the flash photolysis-resonance fluorescence method. The photodecomposition of molecular oxygen provided the oxygen atoms for the experiments. The decay of atomic oxygen was studied on the basis of resonance fluorescence observations. Both reactions investigated were found to be fast processes. A negative temperature dependence of the rate constants for reactions with dimethyl sulfide was observed.
Absolute rate constants of alkoxyl radical reactions in aqueous solution. [Tert-butyl hydroperoxide
Erben-Russ, M.; Michel, C.; Bors, W.; Saran, M.
1987-04-23
The pulse radiolysis technique was used to generate the alkoxyl radical derived from tert-butyl hydroperoxide (/sup t/BuOOH) in aqueous solution. The reactions of this radical with 2,2'-azinobis(3-ethyl-6-benzothiazolinesulfonate) (ABTS) and promethazine were monitored by kinetic spectroscopy. The unimolecular decay rate constant of the tert-butoxyl radical (/sup t/BuO) was determined to be 1.4 x 10/sup 6/ s/sup -1/. On the basis of this value, the rate constants for /sup t/BuO attack on quercetin, crocin, crocetin, ascorbate, isoascorbate, trolox c, glutathione, thymidine, adenosine, guanosine, and unsaturated fatty acids were determined. In addition, the reaction of /sup t/BuO with the polyunsaturated fatty acids (PUFA) was observed by directly monitoring the formation of the fatty acid pentadienyl radicals. Interestingly, the attack of /sup t/BuO on PUFA was found to be faster by about one order of magnitude as compared to the same reaction in a nonpolar solvent.
The rate coefficients of the chemi-ionization processes in slow Li*(n) + Na collisions
NASA Astrophysics Data System (ADS)
Ignjatović, Lj M.; Mihajlov, A. A.; Klyucharev, A. N.
2008-01-01
The semi-classical method for determining the rate coefficients of the chemi-ionization processes in slow non-symmetric atom-Rydberg atom collisions is applied to the Li*(n) + Na case. Calculated rate coefficients are compared with the existing experimental data from the literature. Obtained results have confirmed that resonant mechanism of non-elastic processes in atom-Rydberg atom collisions are fully applicable to non-symmetric chemi-ionization processes. The rate coefficients of such processes in Li*(n) + Na collisions are determined in the regions of principal quantum number and temperature 4 <= n <= 20 and 700 K <= T <= 1100 K which can be of interest for possible further experiments. Also, the potential curves of several lowest Σ states of the molecular ion LiNa+, as well as the values of the square of dipole matrix element for the transition between X2Σ+- and A2Σ+-states, are presented in this paper.
NASA Technical Reports Server (NTRS)
Bogan, Denis
1999-01-01
Laboratory measurements have been carried out to determine low temperature chemical rate coefficients of ethynyl radical (C2H) for the atmospheres of the outer planets and their satellites. This effort is directly related to the Cassini mission which will explore Saturn and Titan. A laser-based photolysis/infrared laser probe setup was used to measure the temperature dependence of kinetic rate coefficients from approx. equal to 150 to 350 K for C2H radicals with H2, C2H2, CH4, CD4, C2H4, C2H6, C3H8, n-C4H10, i-C4H10, neo-C5H12, C3H4 (methylacetylene and allene), HCN, and CH3CN. The results revealed discrepancies of an order of magnitude or more compared with the low temperature rate coefficients used in present models. A new Laval nozzle, low Mach number supersonic expansion kinetics apparatus has been constructed, resulting in the first measurements of neutral C2H radical kinetics at 90 K and permitting studies on condensable gases with insufficient vapor pressure at low temperatures. New studies of C 2H with acetylene have been completed.
NASA Technical Reports Server (NTRS)
Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J.
1984-01-01
The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.
NASA Astrophysics Data System (ADS)
Nilsson, E. J. K.; Joelsson, L. M. T.; Heimdal, J.; Johnson, M. S.; Nielsen, O. J.
2013-12-01
The reaction rate coefficient k(CH3Br + OH) has been determined in the temperature range 298-373 K, using pulse radiolysis/UV kinetic spectroscopy, and at 298 K using a relative rate method. The Arrhenius expression obtained from a fit to the experimental results is (2.9 ± 0.9) × 10-12 exp(-(1230 ± 125)/T) cm3 molecule-1 s-1, which is greater than the expression currently recommended. The relative rate experiments give k(298 K) = (4.13 ± 0.63) × 10-14 cm3 molecule-1 s-1. The results of the absolute and relative rate experiments indicate that the source budget of atmospheric CH3Br should be reinvestigated, as was recently done for CH3Cl.
Derivation of the chemical-equilibrium rate coefficient using scattering theory
NASA Technical Reports Server (NTRS)
Mickens, R. E.
1977-01-01
Scattering theory is applied to derive the equilibrium rate coefficient for a general homogeneous chemical reaction involving ideal gases. The reaction rate is expressed in terms of the product of a number of normalized momentum distribution functions, the product of the number of molecules with a given internal energy state, and the spin-averaged T-matrix elements. An expression for momentum distribution at equilibrium for an arbitrary molecule is presented, and the number of molecules with a given internal-energy state is represented by an expression which includes the partition function.
NASA Technical Reports Server (NTRS)
Jameson, A. R.
1990-01-01
The relationship between the rainfall rate (R) obtained from radiometric brightness temperatures and the extinction coefficient (k sub e) is investigated by computing the values of k sub e over a wide range of rainfall rates, for frequencies from 3 to 25 GHz. The results show that the strength of the relation between the R and the k sub e values exhibits considerable variation for frequencies at this range. Practical suggestions are made concerning the selection of particular frequencies for rain measurements to minimize the error in R determinations.
Gold, Raymond; Roberts, James H.
1989-01-01
A solid state track recording type dosimeter is disclosed to measure the time dependence of the absolute fission rates of nuclides or neutron fluence over a period of time. In a primary species an inner recording drum is rotatably contained within an exterior housing drum that defines a series of collimating slit apertures overlying windows defined in the stationary drum through which radiation can enter. Film type solid state track recorders are positioned circumferentially about the surface of the internal recording drum to record such radiation or its secondary products during relative rotation of the two elements. In another species both the recording element and the aperture element assume the configuration of adjacent disks. Based on slit size of apertures and relative rotational velocity of the inner drum, radiation parameters within a test area may be measured as a function of time and spectra deduced therefrom.
Electron-Ion Recombination Rate Coefficient Measurements in a Flowing Afterglow Plasma
NASA Technical Reports Server (NTRS)
Gougousi, Theodosia; Golde, Michael F.; Johnsen, Rainer
1996-01-01
The flowing-afterglow technique in conjunction with computer modeling of the flowing plasma has been used to determine accurate dissociative-recombination rate coefficients alpha for the ions O2(+), HCO(+), CH5(+), C2H5(+), H3O(+), CO2(+), HCO2(+), HN2O(+), and N2O(+) at 295 K. We find that the simple form of data analysis that was employed in earlier experiments was adequate and we largely confirm earlier results. In the case of HCO(+) ions, published coefficients range from 1.1 X 10(exp -7) to 2.8 x 10(exp -7) cu cm/S, while our measurements give a value of 1.9 x 10(exp -7) cu cm/S.
NASA Technical Reports Server (NTRS)
Leone, Stephen R.
1993-01-01
The objectives are to measure laboratory rate coefficients for key reactions of hydrocarbon molecules and radicals at low temperatures, which are relevant to the atmospheric photochemistry of Saturn, Jupiter, and Titan. Upcoming NASA planetary missions, such as Cassini, will probe the atmosphere of Titan in more detail, offering an excellent opportunity to test kinetic models and to establish fiducial standards for using kinetic models to interpret various parameters of the outer planets. Accurate low temperature kinetic data, which are presently lacking, may require crucial revisions to the rates of formation and destruction and are of utmost importance to the success of these efforts. In this program, several key reactions of ethynyl radicals (C2H) with acetylene (C2H2), methane (CH4), and oxygen (O2), down to temperatures of 170 K were successfully investigated. The experimental apparatus developed in our laboratory for measuring reaction kinetics at low temperatures consists of a laser photolysis/infrared probe laser setup. The rate measurements are carried out as a function of (low) temperature with a transverse flow cell designed specifically for these studies. A 193 nm argon fluoride pulsed excimer laser is used to photolyze a suitable precursor molecule, such as acetylene to produce C2H, and a high resolution, tunable infrared F-center laser (2.3-3.35 mu m) probes the transient concentrations of the radical species directly in absorption to extract the kinetic rate coefficients.
2013-01-01
Background National smoking-specific lung cancer mortality rates are unavailable, and studies presenting estimates are limited, particularly by histology. This hinders interpretation. We attempted to rectify this by deriving estimates indirectly, combining data from national rates and epidemiological studies. Methods We estimated study-specific absolute mortality rates and variances by histology and smoking habit (never/ever/current/former) based on relative risk estimates derived from studies published in the 20th century, coupled with WHO mortality data for age 70–74 for the relevant country and period. Studies with populations grossly unrepresentative nationally were excluded. 70–74 was chosen based on analyses of large cohort studies presenting rates by smoking and age. Variations by sex, period and region were assessed by meta-analysis and meta-regression. Results 148 studies provided estimates (Europe 59, America 54, China 22, other Asia 13), 54 providing estimates by histology (squamous cell carcinoma, adenocarcinoma). For all smoking habits and lung cancer types, mortality rates were higher in males, the excess less evident for never smokers. Never smoker rates were clearly highest in China, and showed some increasing time trend, particularly for adenocarcinoma. Ever smoker rates were higher in parts of Europe and America than in China, with the time trend very clear, especially for adenocarcinoma. Variations by time trend and continent were clear for current smokers (rates being higher in Europe and America than Asia), but less clear for former smokers. Models involving continent and trend explained much variability, but non-linearity was sometimes seen (with rates lower in 1991–99 than 1981–90), and there was regional variation within continent (with rates in Europe often high in UK and low in Scandinavia, and higher in North than South America). Conclusions The indirect method may be questioned, because of variations in definition of smoking and
NASA Astrophysics Data System (ADS)
Nava, D. F.; Mitchell, M. B.; Stief, L. J.
1986-04-01
The absolute rate constant for the reaction H + C4H2 has been measured over the temperature (T) interval 210-423 K, using the technique of flash photolysis-resonance fluorescence. At each of the five temperatures employed, the results were independent of variations in C4H2 concentration, total pressure of Ar or N2, and flash intensity (i.e., the initial H concentration). The rate constant, k, was found to be equal to 1.39 x 10 to the -10th exp (-1184/T) cu cm/s, with an error of one standard deviation. The Arrhenius parameters at the high pressure limit determined here for the H + C4H2 reaction are consistent with those for the corresponding reactions of H with C2H2 and C3H4. Implications of the kinetic carbon chemistry results, particularly those at low temperature, are considered for models of the atmospheric carbon chemistry of Titan. The rate of this reaction, relative to that of the analogous, but slower, reaction of H + C2H2, appears to make H + C4H2 a very feasible reaction pathway for effective conversion of H atoms to molecular hydrogen in the stratosphere of Titan.
Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K
NASA Technical Reports Server (NTRS)
Michael, J. V.; Nava, D. F.; Borokowski, R. P.; Payne, W. A.; Stief, L. J.
1980-01-01
The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.
Technology Transfer Automated Retrieval System (TEKTRAN)
We present near-infrared spectroscopy measurement of absolute cerebral hemoglobin concentration and saturation in a large sample of 36 healthy elderly (mean age, 85 ± 6 years) and 19 young adults (mean age, 28 ± 4 years). Non-invasive measurements were obtained on the forehead using a commercially a...
NASA Technical Reports Server (NTRS)
Judge, Darrell L.
1994-01-01
A prototype spectrometer has been developed for space applications requiring long term absolute EUV photon flux measurements. The energy spectrum of the incoming photons is transformed directly into an electron energy spectrum by taking advantage of the photoelectric effect in one of several rare gases at low pressures. Using an electron energy spectrometer, followed by an electron multiplier detector, pulses due to individual electrons are counted. The overall efficiency of this process can be made essentially independent of gain drifts in the signal path, and the secular degradation of optical components which is often a problem in other techniques is avoided. A very important feature of this approach is its freedom from the problem of overlapping spectral orders that plagues grating EUV spectrometers. An instrument with these features has not been flown before, but is essential to further advances in our understanding of solar EUV flux dynamics, and the coupled dynamics of terrestrial and planetary atmospheres. The detailed characteristics of this optics-free spectrometer are presented in the publications section.
Temperature dependent rate coefficients for the reaction of OH radicals with dimethylbenzoquinones
NASA Astrophysics Data System (ADS)
Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Wenger, John C.
2015-10-01
Rate coefficients for the gas-phase reaction of hydroxyl (OH) radicals with two methylated benzoquinones have been measured at atmospheric pressure over the temperature range 284-313 K using the relative rate method. The following Arrhenius expressions (in cm3 molecule-1 s-1) have been obtained: k(25DMBQ) = (8.59 ± 4.70) × 10-12exp[(228 ± 163)/T] and k(26DMBQ) = (5.11 ± 2.79) × 10-12exp[(399 ± 165)/T] for 2,5-dimethylbenzoquinone (2,5DMBQ) and 2,6-dimethylbenzoquinone (2,6DMBQ), respectively, with corresponding values at 298 K: k(25DMBQ) = (2.05 ± 0.46) × 10-11 and k(26DMBQ) = (1.93 ± 0.12) × 10-11. The rate coefficients are compared to those reported for similar compounds and discussed in terms of structure-activity relationships. The results are also used to calculate atmospheric lifetimes for 2,5DMBQ and 2,6DMBQ with respect to reaction with OH radicals.
Excitation rate coefficients and line ratios for the optical and ultraviolet transitions in S II
NASA Technical Reports Server (NTRS)
Cai, Wei; Pradhan, Anil K.
1993-01-01
New calculations are reported for electron excitation collision strengths, rate coefficients, transition probabilities, and line ratios for the astrophysically important optical and UV lines in S II. The collision strengths are calculated in the close coupling approximation using the R-matrix method. The present calculations are more extensive than previous ones, including all transitions among the 12 lowest LS terms and the corresponding 28 fine-structure levels in the collisional-radiative model for S II. While the present rate coefficients for electron impact excitation are within 10-30 percent of the previous values for the low-lying optical transitions employed as density diagnostics of H II regions and nebulae, the excitation rates for the UV transitions 4S super 0 sub 3/2 - 4Psub 1/2,3/2,5/2 differ significantly from earlier calculations, by up to factor of 2. We describe temperature and density sensitive flux ratios for a number of UV lines. The present UV results are likely to be of interest in a more accurate interpretation of S II emission from the Io plasma torus in the magnetosphere of Jupiter, as well as other UV sources observed from the IUE, ASTRO 1, and the HST.
Optimised geometry to calculate dose rate conversion coefficient for external exposure to photons.
Askri, B; Manai, K; Trabelsi, A; Baccari, B
2008-01-01
A single-parameter geometry to describe soil is achieved for Monte Carlo calculation of absorbed dose rate in air for photon emitters from natural radionuclides. This optimised geometry based on physical assumptions consists of the soil part whose emitted radiation has a given minimum probability to reach the detector. This geometry was implemented in Geant4 toolkit and a significant reduction in computation time was achieved. Simulation tests have shown that for soil represented by a cylinder of 40 m radius and 1 m deep, >98% of the calculated dose rate conversion coefficients in air at 1 m above the ground is generated by only 6% of the soil volume in the case of uniform distribution of radioactivity, and >99.2% of the calculated dose rate for an exponential distribution. When the soil is represented by the entire optimised geometry, 99% of the conversion coefficients values are reached for a soil depth of 1 m and 100% for that of approximately 2 m. PMID:17959610
On the accuracy of the rate coefficients used in plasma fluid models for breakdown in air
NASA Astrophysics Data System (ADS)
Kourtzanidis, Konstantinos; Raja, Laxminarayan L.
2016-07-01
The electrical breakdown of air depends on the balance between creation and loss of charged particles. In fluid models, datasets of the rate coefficients used are obtained either from fits to experimental data or by solutions of the Boltzmann equation. Here, we study the accuracy of the commonly used models for ionization and attachment frequencies and their impact on the prediction of the breakdown threshold for air. We show that large errors can occur depending on the model and propose the most accurate dataset available for modeling of air breakdown phenomena.
NASA Technical Reports Server (NTRS)
Leone, Stephen R.
1992-01-01
The purpose of the project is to perform laboratory measurements of reaction rate coefficients at low temperature. The reactions and temperatures of interest are those that are important in the chemistry of the hydrocarbon rich atmospheres of the outer planets and their satellites. In this stage of the study we are investigating reactions of ethynyl radicals, C2H, with acetylene (C2H2), methane (CH4), and hydrogen (H2). In the previous status report from 24 Jan. 1992, we reported on the development of the experimental apparatus and the first, preliminary data for the C2H + C2H2 reaction.
Vadimova, O L; Mukhin, I B; Kuznetsov, I I; Palashov, O V; Perevezentsev, E A; Khazanov, Efim A
2013-03-31
We have calculated the stored energy and gain coefficient in disk gain elements cooled to cryogenic temperatures. The problem has been solved with allowance for intense heat generation, amplified spontaneous emission and parasitic lasing, without averaging over any spatial coordinate. The numerical simulation results agree well with experimental data, in particular at high heat generation rates. Experimental data and theoretical analysis indicate that composite disk gain elements containing an undoped region can store considerably more energy due to suppression of amplified spontaneous emission and parasitic lasing. (extreme light fields and their applications)
NASA Astrophysics Data System (ADS)
Dickinson, A. S.
2010-11-01
A quantum-reflection model is employed to calculate the rate coefficient for the Penning ionization of rubidium by cold metastable helium atoms in unpolarized collisions. Various results for the p-wave transmission coefficient on a 1/R6 long-range potential are discussed. The dispersion coefficient for the interaction of these atoms is estimated as 3540 au. The calculated value of the rate coefficient is about four times lower than the recently measured value (Byron et al 2010a Phys. Rev. A 81 013405) for this process when both atoms are held in magneto-optical traps.
Determination of the global recombination rate coefficient for the ISX-B Tokamak
Langley, R.A.; Howe, H.C.
1983-01-01
The global recombination rate coefficient for hydrogen has been measured for the ISX-B tokamak vacuum vessel for various surface conditions. The measurements were performed by observing the rate of decrease of gas pressure in the vessel during a glow discharge. The parameters of the glow discharge and the complete experimental method are described. Previously published analytic and numerical models are used for data analysis. The effects of surface contamination on the results are described. For ''unclean'' wall conditions sigmak/sub r/ = 1.8 x 10/sup -28/ cm/sup 4//atom.s at 296 K and increases to sigmak/sub r/ = 4.4 x 10/sup -28/ cm/sup 4//atoms.s for ''clean'' conditions and remains constant until subsequent exposure to air.
High-field measurement of the 129Xe-Cs binary spin-exchange rate coefficient
NASA Astrophysics Data System (ADS)
Jau, Yuan-Yu; Kuzma, Nicholas N.; Happer, William
2004-03-01
We report the first measurement of the binary spin-exchange rate coefficient κ in the ^129Xe-Cs system. Data were taken using ^129Xe NMR in glass cells containing isotopically enriched xenon gas at pressures on the order of atmospheres and a small amount of liquid Cs metal, in the temperature range from 120 to 140^rcC and at a magnetic field of 9.4 T. The contribution of CsXe van der Waals molecules to spin exchange should have been nearly eliminated by the high magnetic field, as confirmed by our measurements of the ^129Xe longitudinal relaxation time T1 in a series of cells with various densities of xenon. The Cs atomic number density [Cs] was controlled by the cell temperature, and was experimentally determined by analysis of the Faraday rotation of linearly polarized probe laser light. We measured κ = d (T_1-1)/d[Cs]= (2.81± 0.2) × 10-16 cm^3 s-1 . This is about 60% larger than the previously measured rate coefficient for the ^129Xe-Rb system(Y.-Y. Jau, N. N. Kuzma, and W. Happer, Phys. Rev. A 66, 052710 (2002).), κ =d (T_1-1)/d[Rb]= (1.75± 0.12) × 10-16 cm^3 s-1 . A comparison with theory(Y.-Y. Jau, N. N. Kuzma, and W. Happer, Phys. Rev. A 67, 022720 (2003).) will be discussed.
Estimating Reaction Rate Coefficients Within a Travel-Time Modeling Framework
Gong, R; Lu, C; Luo, Jian; Wu, Wei-min; Cheng, H.; Criddle, Craig; Kitanidis, Peter K.; Gu, Baohua; Watson, David B; Jardine, Philip M; Brooks, Scott C
2011-03-01
A generalized, efficient, and practical approach based on the travel-time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel-time distribution from the injection point to the observation point. For advection-dominant reactive transport with well-mixed reactive species and a constant travel-time distribution, the reactive BTC is obtained by integrating the solutions to advective-reactive transport over the entire travel-time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero-, first-, nth-order, and Michaelis-Menten reactions. The proposed approach is validated by a reactive transport case in a two-dimensional synthetic heterogeneous aquifer and a field-scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)-bioremediation is better approximated by zero-order reaction kinetics than first-order reaction kinetics.
On the temperature dependence of the rate coefficient of formation of C2+ from C + CH+
NASA Astrophysics Data System (ADS)
Rampino, S.; Pastore, M.; Garcia, E.; Pacifici, L.; Laganà, A.
2016-08-01
We carry out quasi-classical trajectory calculations for the C + CH+→ C_2^+ + H reaction on an ad hoc computed high-level ab initio potential energy surface. Thermal rate coefficients at the temperatures of relevance in cold interstellar clouds are derived and compared with the assumed, temperature-independent estimates publicly available in kinetic data bases KIDA and UDfA. For a temperature of 10 K the data base value overestimates by a factor of 2 the one obtained by us (thus improperly enhancing the destruction route of CH+ in astrochemical kinetic models) which is seen to double in the temperature range 5-300 K with a sharp increase in the first 50 K. The computed values are fitted via the popular Arrhenius-Kooij formula and best-fitting parameters α = 1.32 × 10-9 cm3 s-1, β = 0.1 and γ = 2.19 K to be included in the online mentioned data bases are provided. Further investigation shows that the temperature dependence of the thermal rate coefficient better conforms to the recently proposed so-called `deformed Arrhenius' law by Aquilanti and Mundim.
NASA Technical Reports Server (NTRS)
Leone, Stephen R.
1995-01-01
The objectives of the research are to measure low temperature laboratory rate coefficients for key reactions relevant to the atmospheres of Titan and Saturn. These reactions are, for example, C2H + H2, CH4, C2H2, and other hydrocarbons which need to be measured at low temperatures, down to approximately 150 K. The results of this work are provided to NASA specialists who study modeling of the hydrocarbon chemistry of the outer planets. The apparatus for this work consists of a pulsed laser photolysis system and a tunable F-center probe laser to monitor the disappearance of C2H. A low temperature cell with a cryogenic circulating fluid in the outer jacket provides the gas handling system for this work. These elements have been described in detail in previous reports. Several new results are completed and the publications are just being prepared. The reaction of C2H with C2H2 has been measured with an improved apparatus down to 154 K. An Arrhenius plot indicates a clear increase in the rate coefficient at the lowest temperatures, most likely because of the long-lived (C4H3) intermediate. The capability to achieve the lowest temperatures in this work was made possible by construction of a new cell and addition of a multipass arrangement for the probe laser, as well as improvements to the laser system.
Behavior of rate coefficients for ion-ion mutual neutralization, 300-550 K
Miller, Thomas M.; Shuman, Nicholas S.; Viggiano, A. A.
2012-05-28
Rate coefficients k{sub MN} have been measured for a number of anion neutralization reactions with Ar{sup +} and Kr{sup +} over the temperature range 300-550 K. For the first time, the data set includes anions of radicals and other short-lived species. In the present paper, we review these results and make note of correlations with reduced mass, electron binding energy of the anion (equivalent to the electron affinity of the corresponding neutral), and temperature, and compare with expectations from absorbing sphere models. An intriguing result is that the data for diatomic anions neutralized by Ar{sup +} and Kr{sup +} have k{sub MN} values close to 3 x 10{sup -8} cm{sup 3} s{sup -1} at 300 K, a figure which is lower than those for all of the polyatomic anions at 300 K except for SF{sub 5}{sup -}+ Kr{sup +}. For the polyatomic anions studied here, neutralized by Ar{sup +} and Kr{sup +}, the reduced mass dependence agrees with theory, on average, but we find a stronger temperature dependence of T{sup -0.9} than expected from the theoretical E{sup -0.5} energy dependence of the rate coefficient at thermal energies. The k{sub MN} show a weak dependence on the electron binding energy of the anion for the polyatomic species studied.
Tillis, G.M.; Swain, E.D.
1998-01-01
Discharges through 10 selected coastal control structures in Broward and Palm Beach Counties, Florida, are presently computed using the theoretical discharge-coefficient ratings developed from scale modeling, theoretical discharge coefficients, and some field calibrations whose accuracies for specific sites are unknown. To achieve more accurate discharge-coefficient ratings for the coastal control structures, field discharge measurements were taken with an Acoustic Doppler Current Profiler at the coastal control structures under a variety of flow conditions. These measurements were used to determine computed discharge-coefficient ratings for the coastal control structures under different flow regimes: submerged orifice flow, submerged weir flow, free orifice flow, and free weir flow. Theoretical and computed discharge-coefficient ratings for submerged orifice and weir flows were determined at seven coastal control structures, and discharge ratings for free orifice and weir flows were determined at three coastal control structures. The difference between the theoretical and computed discharge-coefficient ratings varied from structure to structure. The theoretical and computed dischargecoefficient ratings for submerged orifice flow were within 10 percent at four of seven coastal control structures; however, differences greater than 20 percent were found at two of the seven structures. The theoretical and computed discharge-coefficient ratings for submerged weir flow were within 10 percent at three of seven coastal control structures; however, differences greater than 20 percent were found at four of the seven coastal control structures. The difference between theoretical and computed discharge-coefficient ratings for free orifice and free weir flows ranged from 5 to 32 percent. Some differences between the theoretical and computed discharge-coefficient ratings could be better defined with more data collected over a greater distribution of measuring conditions.
Kramers-Moyal coefficients in the analysis and modeling of heart rate variability
NASA Astrophysics Data System (ADS)
Petelczyc, M.; Żebrowski, J. J.; Baranowski, R.
2009-09-01
Modeling of recorded time series may be used as a method of analysis for heart rate variability studies. In particular, the extraction of the first two Kramers-Moyal coefficients has been used in this context. Recently, the method was applied to a wide range of signal analysis: from financial data to physiological and biological time series. Modeling of the signal is important for the prediction and interpretation of the dynamics underlying the process. The method requires the determination of the Markov time. Obtaining the drift and diffusion term of the Kramers-Moyal expansion is crucial for the modeling of the original time series with the Langevin equation. Both Tabar [Comput. Sci. Eng. 8, 54 (2006)] and T. Kuusela [Phys. Rev. E 69, 031916 (2004)] suggested that these terms may be used to distinguish healthy subjects from those with heart failure. The research groups applied a somewhat different methodology and obtained substantially different ranges of the Markov time. We show that the two studies may be considered consistent with each other as Kuusela analyzed 24 h recordings while Tabar analyzed daytime and nighttime recordings, separately. However, both groups suggested using the Langevin equation for modeling of time series which requires the fluctuation force to be a Gaussian. We analyzed heart rate variability recordings for ten young male (age 26-4+3y ) healthy subjects. 24 h recordings were analyzed and 6-h-long daytime and nighttime fragments were selected. Similar properties of the data were observed in all recordings but all the nighttime data and seven of the ten 24 h series exhibited higher-order, non-negligible Kramers-Moyal coefficients. In such a case, the reconstruction of the time series using the Langevin equation is impossible. The non-negligible higher-order coefficients are due to autocorrelation in the data. This effect may be interpreted as a result of a physiological phenomenon (especially occurring for nighttime data): respiratory
Brummelhuis, Walter J; van Schelven, Leonard J; Boer, Walther H
2008-01-01
Methods to continuously measure absolute refill during dialysis are not available. It would be useful to have such a method because it would allow investigating the mechanism of refill the effect of interventions. We designed a feedback algorithm that adjusts ultrafiltration rate (QUF) according to hemoglobin (Hb) concentration changes in such a way that relative blood volume (BV) remains constant within a narrow target range. In this situation, the generated QUF quantitatively reflects refill. Refill patterns were studied in five hypotension prone patients. In addition, on separate occasions, we studied the effect of antiembolism stockings (AES) and infusion of hydroxy-ethylated starch (HAES) on refill in these patients. Refill during the first hour fell significantly from 21 +/- 3 ml/min to 9 +/- 2 ml/min (p < 0.05). In the second hour, refill decreased further and became zero in four out of five patients. Neither AES nor HAES measurably affected refill. The marked and rapid fall in refill in the early stages of dialysis suggests untimely depletion of the interstitial compartment and underestimation of dry weight. We propose that continuous, online measurement of refill patterns may be of value for accurate estimation of dry weight in dialysis patients. PMID:18204322
Characterization of the reaction rate coefficient of DNA with the hydroxyl radical
Milligan, J.R.; Ward, J.F.; Aguilera, J.A.
1996-11-01
Using agarose gel electrophoresis, we have measured the yield of single-strand breaks (SSBs) induced by {sup 137}Cs {gamma} irradiation in a variety of plasmid DNA substrates ranging in size from 2.7 kb to 38 kb irradiated in aerobic aqueous solution in the presence of the hydroxyl radical scavenger dimethyl sulfoxide (DMSO). Under these conditions DNA SSBs are caused mainly by the hydroxyl radical. Using the competition between DMSO and DNA for the hydroxyl radical, we have estimated the rate coefficient for the reaction of the hydroxyl radical with DNA. The results cannot be characterized by conventional steady-state competition kinetics. However, it is possible to describe the second-order rate constant for the reaction as a function of the scavenging capacity of the solution. The second-order rate constant increases with increasing scavenging capacity, rising from about 5x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at 10{sup 5} s{sup -1} to about 10{sup 10} dm{sup 3} mol{sup -1} s{sup -1} at 10{sup 10} s{sup -1}. This dependence of the second-order rate constant on the scavenging capacity appears to be more pronounced for larger plasmids. 17 refs., 4 figs.
Revised rate coefficients for H2 and H- destruction by realistic stellar spectra
NASA Astrophysics Data System (ADS)
Agarwal, Bhaskar; Khochfar, Sadegh
2015-01-01
Understanding the processes that can destroy H2 and H- species is quintessential in governing the formation of the first stars, black holes and galaxies. In this study, we compute the reaction rate coefficients for H2 photodissociation by Lyman-Werner photons (11.2-13.6 eV) and H- photodetachment by 0.76 eV photons emanating from self-consistent stellar populations that we model using publicly available stellar synthesis codes. So far, studies that include chemical networks for the formation of molecular hydrogen take these processes into account by assuming that the source spectra can be approximated by a power-law dependence or a blackbody spectrum at 104 or 105 K. We show that using spectra generated from realistic stellar population models can alter the reaction rates for photodissociation, kdi, and photodetachment, kde, significantly. In particular, kde can be up to ˜2-4 orders of magnitude lower in the case of realistic stellar spectra suggesting that previous calculations have overestimated the impact that radiation has on lowering H2 abundances. In contrast to burst modes of star formation, we find that models with continuous star formation predict increasing kde and kdi, which makes it necessary to include the star formation history of sources to derive self-consistent reaction rates, and that it is not enough to just calculate J21 for the background. For models with constant star formation rate, the change in shape of the spectral energy distribution leads to a non-negligible late-time contribution to kde and kdi, and we present self-consistently derived cosmological reaction rates based on star formation rates consistent with observations of the high-redshift Universe.
Cowin, S C; Hart, R T; Balser, J R; Kohn, D H
1985-01-01
In this paper we describe a computational means, based on beam theory, for application of the theory of adaptive elasticity to examples of real bone geometries. The results of the animal experiments were taken from the literature, and each documented the temporal evolution of a change in bone shape after a significant change in the mechanical loading environment of the bone. For each of these studies, we establish preliminary estimates of the in vivo values of the surface remodeling rate coefficients--the key parameters in the theory of surface remodeling. Our preliminary parameter estimates are established by comparison of published animal experimental results with surface remodeling theory predictions generated by the computational method. PMID:4077864
Temperature dependence of the atmospheric photolysis rate coefficient for NO2
NASA Technical Reports Server (NTRS)
Shetter, Richard E.; Davidson, James A.; Cantrell, Christopher A.; Burzysnki, Norbert J., Jr.; Calvert, Jack G.
1988-01-01
Accurate values for the photolysis rate coefficient of NO2 (j1) are required for studies related to the observed imbalance in the photostationary state of O3, NO, and NO2 in the troposphere. Direct measurements of the temperature dependence of j1 at temperatures from -70 to 30 C were made in sunlight for relatively cloudless summer days in Boulder, Colorado. The ratios of j1 (30 C)/j1 (T C) for T = -10 C and -70 C, respectively, were 1.046 + or - 0.040 and 1.070 + or - 0.031. The j1 ratios were independent of solar zenith angle. Theoretical estimates of the temperature-dependent j1 ratios based upon recently reported cross section (sigma) and quantum yield (phi) data are more consistent with these experimental measurements than those based upon the currently accepted sigma and phi data.
NASA Technical Reports Server (NTRS)
Chackerian, Charles, Jr.; Freedman, R.; Giver, L. P.; Brown, L. R.
2001-01-01
The rotationless transition moment squared for the x(sup 1) sigma (sup +) v=3 (left arrow) v=0 band of CO is measured to be the absolute value of R (sub 3-0) squared = 1.7127(25)x 10(exp -7) Debye squared. This value is about 8.6 percent smaller than the value assumed for HITRAN 2000. The Herman-Wallis intensity factor of this band is F=1+0.01168(11)m+0.0001065(79)m squared. The determination of self-broadening coefficients is improved with the inclusion of line narrowing; self-shifts are also reported.
Determination of collisional quenching rate coefficient of N2(A^3σu^+ )
NASA Astrophysics Data System (ADS)
Koizumi, Yuusuke; Suzuki, Susumu; Itoh, Haruo
2012-10-01
We have previously determined the collisional quenching rate coefficient of N2(A^3σu^+ ) by an air pollutant gas [1-4]. In this paper we report the collisional quenching rate coefficient k' of N2(A^3σu^+ ) by p-xylene (C8H10), which was determined to be (6.5±0.9)x10-9 cm^3/s. In addition, through repeated experiments it was found that by-products of p-xylene were deposited on the cathode, similarly to the cases of m-xylene and o-xylene previously reported [4], and then the current-voltage curves consistently shifed to a higher-E/p0 region. To clarify the reason for this behavior, we confirmed by Auger electron spectroscopy (AES) and Fourier transform infrared spectroscopy (FTIR) that these changes in the current-voltage curves were caused by the deposition of a thin film of by-product of decomposed xylene on the cathode surface. According to the results of AES, C atoms were detected in a sample exposed to an electrical discharge, and we confirmed that the deposit of C was thickest in the case of electrical discharge in p-xylene. According to the results of FTIR, it was found that CH2 and CH were obtained from the deposition of p-xylene. [4pt] [1] S. Suzuki, H. Itoh, H. Sekizawa and N. Ikuta, J. Phys. Soc. Jpn., 62, No.8, 2692-2697 (1993)[0pt] [2] S. Suzuki, H. Itoh, H. Sekizawa and N. Ikuta, Jpn. J. Appl. Phys., 36, 4744-4746 (1997)[0pt] [3] S. Suzuki, T. Suzuki and H. Itoh, Cont. of HAKONE X Saga, Japan, 132-135 (2006)[0pt] [4] S. Suzuki, H. Itoh, Proc. of 30th ICPIG (Belfast, UK), A1-12 (2011)
Distribution coefficients (Kd) and desorption rates of 137Cs and 241Am in Black Sea sediments.
Topcuoğlu, S; Güngör, N; Kirbaşoğlu, C
2002-12-01
The distribution coefficients (Kd) and desorption rates of 137Cs and 241Am radionuclides in bottom sediments at different locations in the Black Sea were studied under laboratory conditions. The Kd values were found to be 500 for 137Cs and 3800 for 241Am at the steady state and described exponential curves. Rapid uptake of the radionuclides occurred during the initial period and little accumulation happened after four days. The desorption rates for 137Cs in different bottom sediments were best described by a three-component exponential model. The desorption half-times of 137Cs ranged from 26 to 50 d at the slow components. However, the desorption rate of 241Am described one component for all sediment samples and desorption half-time was found to be 75 d. In general, the results showed that the 241Am radionuclide is more effectively transferred to bottom sediment and has longer turnover time than 137Cs under Black Sea conditions. PMID:12489734
Laporta, V.; Celiberto, R.; Tennyson, J.
2014-12-09
Rate coefficients for dissociative electron attachment and electron-impact dissociation processes, involving vibrationally excited molecular oxygen, are presented. Analytical fits of the calculated numerical data, useful in the applications, are also provided.
New potential energy surface for the HCS{sup +}–He system and inelastic rate coefficients
Dubernet, Marie-Lise; Quintas-Sánchez, Ernesto; Tuckey, Philip
2015-07-28
A new high quality potential energy surface is calculated at a coupled-cluster single double triple level with an aug-cc-pV5Z basis set for the HCS{sup +}–He system. This potential energy surface is used in low energy quantum scattering calculations to provide a set of (de)-excitation cross sections and rate coefficients among the first 20 rotational levels of HCS{sup +} by He in the range of temperature from 5 K to 100 K. The paper discusses the impact of the new ab initio potential energy surface on the cross sections at low energy and provides a comparison with the HCO{sup +}–He system. The HCS{sup +}–He rate coefficients for the strongest transitions differ by factors of up to 2.5 from previous rate coefficients; thus, analysis of astrophysical spectra should be reconsidered with the new rate coefficients.
Klein, L; Lemel, M S; Wolfe, M S; Shaffer, J
1994-10-01
The weanling rat, an animal model of rapid bone turnover, was used to evaluate the effects of various doses of cyclosporin A (CsA) on various bones during different time periods. Sprague-Dawley male rats were extensively prelabeled with 3H-tetracycline during 1-3 weeks of age. At 4 weeks of age, four groups of rats were given daily subcutaneous injections: vehicle or CsA--low dose (10 mg/kg), intermediary dose (20 mg/kg), or high dose (30 mg/kg) for 7, 14, or 28 days. Three different whole bones--the femur (low turnover), scapula (moderate turnover), and lumbar-6 vertebra (high turnover) were harvested intact at 4, 5, 6, and 8 weeks of age. The whole bones were assayed weekly for total dry defatted weight, calcium mass (formation), and loss of 3H-tetracycline (bone resorption) following treatment with CsA. Serum CsA levels, calcium creatinine, and alkaline phosphatase were measured weekly. Significant decreases in serum calcium and alkaline phosphatase were observed at 1 and 2 weeks, and were normalized by 4 weeks of treatment. No significant changes in serum creatinine were noted. For all three doses of CsA, no effect was observed on the absolute rate of cortical bone resorption of three different, whole bones over three time periods. Body weight and bone formation in treated animals was significantly smaller in a dose- and time-related fashion compared with control animals at sacrifice. However, compared with the initial control animals, body weights and bone masses of the final treated animals were much larger, suggesting that the smaller bone masses were due to insufficient growth and slow gain in bone mass.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7820781
Gómez-Carrasco, Susana; Godard, Benjamin; Lique, François; Bulut, Niyazi; Kłos, Jacek; Roncero, Octavio; Aguado, Alfredo; Aoiz, F. Javier; Castillo, Jesús F.; Goicoechea, Javier R.; Etxaluze, Mireya; Cernicharo, José
2014-10-10
The rate constants required to model the OH{sup +} observations in different regions of the interstellar medium have been determined using state of the art quantum methods. First, state-to-state rate constants for the H{sub 2}(v = 0, J = 0, 1) + O{sup +}({sup 4} S) → H + OH{sup +}(X {sup 3}Σ{sup –}, v', N) reaction have been obtained using a quantum wave packet method. The calculations have been compared with time-independent results to assess the accuracy of reaction probabilities at collision energies of about 1 meV. The good agreement between the simulations and the existing experimental cross sections in the 0.01-1 eV energy range shows the quality of the results. The calculated state-to-state rate constants have been fitted to an analytical form. Second, the Einstein coefficients of OH{sup +} have been obtained for all astronomically significant rovibrational bands involving the X {sup 3}Σ{sup –} and/or A {sup 3}Π electronic states. For this purpose, the potential energy curves and electric dipole transition moments for seven electronic states of OH{sup +} are calculated with ab initio methods at the highest level, including spin-orbit terms, and the rovibrational levels have been calculated including the empirical spin-rotation and spin-spin terms. Third, the state-to-state rate constants for inelastic collisions between He and OH{sup +}(X {sup 3}Σ{sup –}) have been calculated using a time-independent close coupling method on a new potential energy surface. All these rates have been implemented in detailed chemical and radiative transfer models. Applications of these models to various astronomical sources show that inelastic collisions dominate the excitation of the rotational levels of OH{sup +}. In the models considered, the excitation resulting from the chemical formation of OH{sup +} increases the line fluxes by about 10% or less depending on the density of the gas.
Ar II Emission Processes and Emission Rate Coefficients in ASTRAL Helicon Plasmas
NASA Astrophysics Data System (ADS)
Boivin, R. F.; Gardner, A.; Kamar, O.; Kesterson, A.; Loch, S.; Munoz, J.; Ballance, C.
2008-11-01
Emission processes for Ar II line emission are described for low temperature plasmas (Te < 10 eV). It is found that Ar II emission results primarily from Ar ion ground state excitation rather than from any Ar neutral state. This suggests that Ar II emission results from stepping processes which includes ionization and then excitation of the neutral Ar atom filling the vacuum chamber. The Ar II emission rate coefficients are measured in the ASTRAL helicon plasma source using a 0.33 m monochromator and a CCD camera. ASTRAL produces Ar plasmas with the following parameters: ne = 1E11 -- 1E13 cm-3 and Te = 2 - 10 eV, B-field <= 1.3 kGauss, rf power <= 2 kWatt. RF compensated Langmuir probes are used to measure Te and ne. In this experiment, Ar II transitions are monitored as a function of Te while ne is kept constant. Experimental emission rates are obtained as a function of Te and compared to theoretical predictions. Theoretical predictions make use of the ADAS suite of codes as well as recent R-matrix electron-impact excitation calculations that includes pseudo-states contributions. Our collisional-radiative formalism assumes that the excited levels are in quasi-static equilibrium with the ground and metastable populations.
Batorsky, Rebecca; Kearney, Mary F.; Palmer, Sarah E.; Maldarelli, Frank; Rouzine, Igor M.; Coffin, John M.
2011-01-01
HIV adaptation to a host in chronic infection is simulated by means of a Monte-Carlo algorithm that includes the evolutionary factors of mutation, positive selection with varying strength among sites, random genetic drift, linkage, and recombination. By comparing two sensitive measures of linkage disequilibrium (LD) and the number of diverse sites measured in simulation to patient data from one-time samples of pol gene obtained by single-genome sequencing from representative untreated patients, we estimate the effective recombination rate and the average selection coefficient to be on the order of 1% per genome per generation (10−5 per base per generation) and 0.5%, respectively. The adaptation rate is twofold higher and fourfold lower than predicted in the absence of recombination and in the limit of very frequent recombination, respectively. The level of LD and the number of diverse sites observed in data also range between the values predicted in simulation for these two limiting cases. These results demonstrate the critical importance of finite population size, linkage, and recombination in HIV evolution. PMID:21436045
Regression Splines in the Time-Dependent Coefficient Rates Model for Recurrent Event Data
Amorim, Leila D.; Cai, Jianwen; Zeng, Donglin; Barreto, Maurício L.
2009-01-01
SUMMARY Many epidemiologic studies involve the occurrence of recurrent events and much attention has been given for the development of modelling techniques that take into account the dependence structure of multiple event data. This paper presents a time-dependent coefficient rates model that incorporates regression splines in its estimation procedure. Such method would be appropriate in situations where the effect of an exposure or covariates changes over time in recurrent event data settings. The finite sample properties of the estimators are studied via simulation. Using data from a randomized community trial that was designed to evaluate the effect of vitamin A supplementation on recurrent diarrheal episodes in small children, we model the functional form of the treatment effect on the time to the occurrence of diarrhea. The results describe how this effect varies over time. In summary, we observed a major impact of the vitamin A supplementation on diarrhea after 2 months of the dosage, with the effect diminishing after the third dosage. The proposed method can be viewed as a flexible alternative to the marginal rates model with constant effect in situations where the effect of interest may vary over time. PMID:18696748
Coughlin, Jeffrey L.; Harrison, Thomas E.; Gelino, Dawn M.
2010-11-10
We present a novel technique to determine the absolute inclination of single stars using multi-wavelength submilliarcsecond astrometry. The technique exploits the effect of gravity darkening, which causes a wavelength-dependent astrometric displacement parallel to a star's projected rotation axis. We find that this effect is clearly detectable using SIM Lite for various giant stars and rapid rotators, and present detailed models for multiple systems using the REFLUX code. We also explore the multi-wavelength astrometric reflex motion induced by spots on single stars. We find that it should be possible to determine spot size, relative temperature, and some positional information for both giant and nearby main-sequence stars utilizing multi-wavelength SIM Lite data. These data will be extremely useful in stellar and exoplanet astrophysics, as well as supporting the primary SIM Lite mission through proper multi-wavelength calibration of the giant star astrometric reference frame, and reduction of noise introduced by starspots when searching for extrasolar planets.
Determination of the reaction rate coefficient of sulphide mine tailings deposited under water.
Awoh, Akué Sylvette; Mbonimpa, Mamert; Bussière, Bruno
2013-10-15
The efficiency of a water cover to limit dissolved oxygen (DO) availability to underlying acid-generating mine tailings can be assessed by calculating the DO flux at the tailings-water interface. Fick's equations, which are generally used to calculate this flux, require knowing the effective DO diffusion coefficient (Dw) and the reaction (consumption) rate coefficient (Kr) of the tailings, or the DO concentration profile. Whereas Dw can be accurately estimated, few studies have measured the parameter Kr for submerged sulphide tailings. The objective of this study was to determine Kr for underwater sulphide tailings in a laboratory experiment. Samples of sulphide mine tailings (an approximately 6 cm layer) were placed in a cell under a water cover (approximately 2 cm) maintained at constant DO concentration. Two tailings were studied: TA1 with high sulphide content (83% pyrite) and TA2 with low sulphide content (2.8% pyrite). DO concentration was measured with a microelectrode at various depths above and below the tailings-water interface at 1 mm intervals. Results indicate that steady-state condition was rapidly attained. As expected, a diffusive boundary layer (DBL) was observed in all cases. An iterative back-calculation process using the numerical code POLLUTEv6 and taking the DBL into account provided the Kr values used to match calculated and experimental concentration profiles. Kr obtained for tailings TA1 and TA2 was about 80 d(-1) and 6.5 d(-1), respectively. For comparison purposes, Kr obtained from cell tests on tailings TA1 was lower than Kr calculated from the sulphate production rate obtained from shake-flask tests. Steady-state DO flux at the water-tailings interface was then calculated with POLLUTEv6 using tailings characteristics Dw and Kr. For the tested conditions, DO flux ranged from 608 to 758 mg O2/m(2)/d for tailings TA1 and from 177 to 221 mg O2/m(2)/d for tailings TA2. The impact of placing a protective layer of inert material over
Ionization cross sections and rate coefficients for CFCl3 molecule by electron impact
NASA Astrophysics Data System (ADS)
Pal, Satyendra; Kumar, Neeraj
2013-09-01
Chlorofluorocarbons (CFCs) or freons are important industrial material with wide-ranging applications as refrigerant, aerosol propellant and semiconductor etchant, etc. The large-scale industrial consumption is of particular environmental concern because of its potential for ozone destruction in the stratosphere. The present work reports the calculations for differential cross sections as a function of secondary/ ejected electron energy and the scattering angle in the ionization of CFCl3 by electron collision leading to the production of various cations viz. CCl3+,CFCl2+,CCl2+,CFCl+, CCl+, Cl+, CF+, F+, and C+ through direct and dissociative ionization processes at a fixed incident electron energy of 200 eV. A modified Jain-Khare semi-empirical formalism based on oscillator strength has been employed. To the best of our knowledge, no experimental and/or theoretical data is available for comparison of the present results for differential cross sections. The corresponding derived integral cross sections in terms of the partial ionization cross sections corresponding to these cations, in the energy range varying from ionization threshold to 1000 eV, revealed a reasonably good agreement with the experimental and theoretical data, wherever available. In addition to the differential and integral ionization cross sections, we have also calculated the ionization rate coefficients using the evaluated partial ionization cross sections and the Maxwell-Boltzmann distribution as a function of electron energy.
Electron Impact Ionization Cross Sections and Rate Coefficients for Single Carbon Freon Molecules
NASA Astrophysics Data System (ADS)
Pal, Satyendra; Kumar, Neeraj
2015-09-01
Single carbon Freon molecules or chlorofluorocarbons (CFCs) are important industrial material with wide-ranging applications as refrigerant, aerosol propellant and semiconductor etchant, etc. The large-scale industrial consumption is of particular environmental concern because of its potential for ozone destruction in the stratosphere. In the present work, we have extended and generalized the modified Jain-Khare (JK) semi-empirical formalism for the evaluation of the total ionization cross sections corresponding to the formation of the cations in the electron impact ionization of molecules to the electron impact ionization of single carbon freon molecules, viz. CFCl3, CF2Cl2 and CF3Cl. The integral partial and the total ionization cross sections as function of incident electron energy are evaluated in the energy range varying from ionization threshold to 1000 eV. In absence of available differential cross sections, the corresponding derived partial and total ionization cross sections revealed a reasonably good agreement with the experimental and theoretical data, wherever available. In addition to the differential and integral ionization cross sections, we have also calculated the ionization rate coefficients using the evaluated partial ionization cross sections and the Maxwell-Boltzmann distribution as a function of electron temperature/energy. The work is supported by DST, New Delhi, India.
Cranor, W.L.; Alvarez, D.A.; Huckins, J.N.; Petty, J.D.
2009-01-01
To fully utilize semipermeable membrane devices (SPMDs) as passive samplers in air monitoring, data are required to accurately estimate airborne concentrations of environmental contaminants. Limited uptake rate constants (kua) and no SPMD air partitioning coefficient (Ksa) existed for vapor-phase contaminants. This research was conducted to expand the existing body of kinetic data for SPMD air sampling by determining kua and Ksa for a number of airborne contaminants including the chemical classes: polycyclic aromatic hydrocarbons, organochlorine pesticides, brominated diphenyl ethers, phthalate esters, synthetic pyrethroids, and organophosphate/organosulfur pesticides. The kuas were obtained for 48 of 50 chemicals investigated and ranged from 0.03 to 3.07??m3??g-1??d-1. In cases where uptake was approaching equilibrium, Ksas were approximated. Ksa values (no units) were determined or estimated for 48 of the chemicals investigated and ranging from 3.84E+5 to 7.34E+7. This research utilized a test system (United States Patent 6,877,724 B1) which afforded the capability to generate and maintain constant concentrations of vapor-phase chemical mixtures. The test system and experimental design employed gave reproducible results during experimental runs spanning more than two years. This reproducibility was shown by obtaining mean kua values (n??=??3) of anthracene and p,p???-DDE at 0.96 and 1.57??m3??g-1??d-1 with relative standard deviations of 8.4% and 8.6% respectively.
NASA Astrophysics Data System (ADS)
Cranor, Walter L.; Alvarez, David A.; Huckins, James N.; Petty, Jimmie D.
To fully utilize semipermeable membrane devices (SPMDs) as passive samplers in air monitoring, data are required to accurately estimate airborne concentrations of environmental contaminants. Limited uptake rate constants ( kua) and no SPMD air partitioning coefficient ( Ksa) existed for vapor-phase contaminants. This research was conducted to expand the existing body of kinetic data for SPMD air sampling by determining kua and Ksa for a number of airborne contaminants including the chemical classes: polycyclic aromatic hydrocarbons, organochlorine pesticides, brominated diphenyl ethers, phthalate esters, synthetic pyrethroids, and organophosphate/organosulfur pesticides. The kuas were obtained for 48 of 50 chemicals investigated and ranged from 0.03 to 3.07 m 3 g -1 d -1. In cases where uptake was approaching equilibrium, Ksas were approximated. Ksa values (no units) were determined or estimated for 48 of the chemicals investigated and ranging from 3.84E+5 to 7.34E+7. This research utilized a test system (United States Patent 6,877,724 B1) which afforded the capability to generate and maintain constant concentrations of vapor-phase chemical mixtures. The test system and experimental design employed gave reproducible results during experimental runs spanning more than two years. This reproducibility was shown by obtaining mean kua values ( n = 3) of anthracene and p, p'-DDE at 0.96 and 1.57 m 3 g -1 d -1 with relative standard deviations of 8.4% and 8.6% respectively.
Rowley, R.L.; Adams, M.E.; Marshall, T.L.; Oscarson, J.L.; Wilding, W.V.; Anderson, D.J.
1997-03-01
Natural gas processors use amine treating processes to remove the acid gases H{sub 2}S and CO{sub 2} from gas streams. Absorption rates of gaseous CO{sub 2} into aqueous N-methyldiethanolamine (MDEA) solutions were measured in a quiescent, inverted-tube diffusiometer by monitoring the rate of pressure drop. The absorption rate was found to be insensitive to the diffusion coefficient of CO{sub 2} in solution but very sensitive to the diffusion rate of bicarbonate and protonated MDEA ions. Evidence also suggested that chemical reaction equilibrium is rapid relative to diffusion. A numerical model was developed on the basis of these observations. The model was used to regress diffusion coefficients of bicarbonate and protonated amine, which must be equivalent by electroneutrality arguments, from measured absorption rates. Complete modeling of the absorption process also required data for the diffusion coefficient of MDEA in water. These were measured using a Taylor dispersion apparatus. CO{sub 2} absorption rates and diffusion coefficients of bicarbonate and protonated MDEA were obtained at 298.2 K and 318.2 K in solutions containing 20, 35, and 50 mass % MDEA in water.
NASA Technical Reports Server (NTRS)
Eckardt, Robert C.; Byer, Robert L.; Masuda, Hisashi; Fan, Yuan Xuan
1990-01-01
Both absolute and relative nonlinear optical coefficients of six nonlinear materials measured by second-harmonic generation are discussed. A single-mode, injection-seeded, Q-switched Nd:YAG laser with spatially filtered output was used to generate the 1.064-micron fundamental radiation. The following results were obtained: d36(KDP) = 0.38 pm/V, d36(KD/asterisk/P) = 0.37 pm/V, (parallel)d22(BaB2O4)(parallel) = 2.2 pm/V, d31(LiIO3) = -4.1 pm/V, d31(5 percentMgO:MgO LiNbO3) = -4.7 pm/V, and d(eff)(KTP) = 3.2 pm/V. The accuracy of these measurements is estimated to be better than 10 percent.
Rate Coefficients of the HCl + OH → Cl + H2O Reaction from Ring Polymer Molecular Dynamics.
Zuo, Junxiang; Li, Yongle; Guo, Hua; Xie, Daiqian
2016-05-26
Thermal rate coefficients at temperatures between 200 and 1000 K are calculated for the HCl + OH → Cl + H2O reaction on a recently developed permutation invariant potential energy surface, using ring polymer molecular dynamics (RPMD). Large deviations from the Arrhenius limit are found at low temperatures, suggesting significant quantum tunneling. Agreement with available experimental rate coefficients is generally satisfactory, although the deviation becomes larger at lower temperatures. The theory-experiment discrepancy is attributed to the remaining errors in the potential energy surface, which is known to slightly overestimate the barrier. In the deep tunneling region, RPMD performs better than traditional transition-state theory with semiclassical tunneling corrections. PMID:27149243
NASA Astrophysics Data System (ADS)
Denisov, Vasilii
2016-08-01
In this report, we study sufficient conditions on the lower order coefficients of a parabolic equation guaranteeing the power rate of the uniform stabilization to zero of the solution to the Cauchy problem on every compact K in RN and for any bounded initial function.
Two second-order transformation rate coefficients--kb, based on total plate counts, and kA, based on periphyton-colonized surface areas--were used to compare xenobiotic chemical transformation by laboratory-developed (microcosm) and by field-collected microbiota. Similarity of tr...
NASA Technical Reports Server (NTRS)
Torr, M. R.; Torr, D. G.
1980-01-01
Using a data base of aeronomical parameters measured on board the Atmosphere Explorer-C satellite, temperature dependence of the reaction rate coefficient is deduced for the charge exchange of O(+)(2D) with N2. The results indicate the Explorer values determined over the temperature range from 700 to 1900 K are not in conflict with laboratory measurements made at higher temperatures.
NASA Technical Reports Server (NTRS)
Savin, D. W.; Gwinner, G.; Schwalm, D.; Wolf, A.; Mueller, A.; Schippers, S.
2002-01-01
Low temperature dielectronic recombination (DR) is the dominant recombination mechanism for most ions in X-ray photoionized cosmic plasmas. Reliably modeling and interpreting spectra from these plasmas requires accurate low temperature DR rate Coefficients. Of particular importance are the DR rate coefficients for the iron L-shell ions (Fe XVII-Fe XXIV). These ions are predicted to play an important role in determining the thermal structure and line emission of X-ray photoionized plasmas, which form in the media surrounding accretion powered sources such as X-ray binaries (XRBs), active galactic nuclei (AGN), and cataclysmic variables (Savin et al., 2000). The need for reliable DR data of iron L-shell ions has become particularly urgent after the launches of Chandra and XMM-Newton. These satellites are now providing high-resolution X-ray spectra from a wide range of X-ray photoionized sources. Interpreting the spectra from these sources requires reliable DR rate coefficients. However, at the temperatures relevant, for X-ray photoionized plasmas, existing theoretical DR rate coefficients can differ from one another by factors of two to orders of magnitudes.
NASA Technical Reports Server (NTRS)
Herbst, E.; Leung, C. M.
1986-01-01
In order to incorporate large ion-polar neutral rate coefficients into existing gas phase reaction networks, it is necessary to utilize simplified theoretical treatments because of the significant number of rate coefficients needed. The authors have used two simple theoretical treatments: the locked dipole approach of Moran and Hamill for linear polar neutrals and the trajectory scaling approach of Su and Chesnavich for nonlinear polar neutrals. The former approach is suitable for linear species because in the interstellar medium these are rotationally relaxed to a large extent and the incoming charged reactants can lock their dipoles into the lowest energy configuration. The latter approach is a better approximation for nonlinear neutral species, in which rotational relaxation is normally less severe and the incoming charged reactants are not as effective at locking the dipoles. The treatments are in reasonable agreement with more detailed long range theories and predict an inverse square root dependence on kinetic temperature for the rate coefficient. Compared with the locked dipole method, the trajectory scaling approach results in rate coefficients smaller by a factor of approximately 2.5.
NASA Astrophysics Data System (ADS)
Savin, D. W.; Gwinner, G.; Schwalm, D.; Wolf, A.; Müller, A.; Schippers, S.
2002-11-01
Low temperature dielectronic recombination (DR) is the dominant recombination mechanism for most ions in X-ray photoionized cosmic plasmas. Reliably modeling and interpreting spectra from these plasmas requires accurate low temperature DR rate coefficients. Of particular importance are the DR rate coefficients for the iron L-shell ions (Fe XVII -Fe XXIV). These ions are predicted to play an important role in determining the thermal structure and line emission of X-ray photoionized plasmas, which form in the media surrounding accretion powered sources such as X-ray binaries (XRBs), active galactic nuclei (AGN), and cataclysmic variables (Savin et al. 2000). The need for reliable DR data of iron L-shell ions has become particularly urgent after the launches of Chandra and XMM-Newton. These satellites are now providing high-resolution X-ray spectra from a wide range of X-ray photoionized sources. Interpreting the spectra from these sources requires reliable DR rate coefficients. However, at the temperatures relevant for X-ray photoionized plasmas, existing theoretical DR rate coefficients can differ from one another by factors of two to orders of magnitudes. To address the need for accurate low temperature DR rate coefficients of the iron L-shell ions, we have initiated a program of measurements for DR via 2 to 2 core excitations using the heavy-ion Test Storage Ring located at the Max-Planck-Institute for Nuclear Physics in Heidelberg, Germany. To date measurements have been carried out for Fe XVIII (Savin et al. 1997, 1999), Fe XIX (Savin et al. 1999), Fe XX (Savin et al. 2002), Fe XXI, Fe XXII, and Fe XXIV. Here we review our work to date, discuss the implications of our results, and map out our future research efforts. This work was supported in part by NASA SARA Program grant NAG5-5261, the German Federal Minister for Education and Research (BMBF), and the German Research Council (DFG).
LABORATORY STUDY OF RATE COEFFICIENTS FOR H{sub 2}O:He INELASTIC COLLISIONS BETWEEN 20 AND 120 K
Tejeda, G.; Moreno, E.; Fernández, J. M.; Montero, S.; Carmona-Novillo, E.; Hernández, M. I.
2015-01-01
State-to-state rate coefficients for ortho-H{sub 2}O:He and para-H{sub 2}O:He inelastic collisions in the 20-120 K thermal range are investigated by means of an improved experimental procedure. This procedure is based on the use of a kinetic master equation (MEQ) which describes the evolution of populations of H{sub 2}O rotational levels along a supersonic jet of H{sub 2}O highly diluted in helium. The MEQ is expressed in terms of experimental observables and rate coefficients for H{sub 2}O:He inelastic collisions. The primary experimental observables are the local number density and the populations of the rotational energy levels of H{sub 2}O, quantities which are determined along the jet with unprecedented accuracy by means of Raman spectroscopy with high space resolution. Sets of rate coefficients from the literature and from present close-coupling calculations using two different potential energy surfaces (PESs) have been tested against the experiment. The Green et al. rate coefficients are up to 50% too low compared to the experiment, while most rates calculated here from the Hodges et al. PES and the Patkowski et al. PES are much closer to the experimental values. Experimental rates with an estimated accuracy on the order of 10% have been obtained for ortho-H{sub 2}O:He and para-H{sub 2}O:He inelastic collisions between 20 and 120 K by scaling and averaging the theoretical rates to the experiment.
NASA Astrophysics Data System (ADS)
Donnelly, Russell J.; Sheibley, D.; Belloni, M.; Stamper-Kurn, D.; Vinen, W. F.
2006-12-01
Absolute Zero is a two hour PBS special attempting to bring to the general public some of the advances made in 400 years of thermodynamics. It is based on the book “Absolute Zero and the Conquest of Cold” by Tom Shachtman. Absolute Zero will call long-overdue attention to the remarkable strides that have been made in low-temperature physics, a field that has produced 27 Nobel Prizes. It will explore the ongoing interplay between science and technology through historical examples including refrigerators, ice machines, frozen foods, liquid oxygen and nitrogen as well as much colder fluids such as liquid hydrogen and liquid helium. A website has been established to promote the series: www.absolutezerocampaign.org. It contains information on the series, aimed primarily at students at the middle school level. There is a wealth of material here and we hope interested teachers will draw their student’s attention to this website and its substantial contents, which have been carefully vetted for accuracy.
Payne, Walter A.; Harding, Lawrence B.; Stief, Louis J.; Parker, James F. , 1925-; Klippenstein, Stephen J.; Nesbitt, Fred L.; Cody, Regina J.
2004-10-01
The rate coefficient has been measured under pseudo-first-order conditions for the Cl + CH{sub 3} association reaction at T = 202, 250, and 298 K and P = 0.3-2.0 Torr helium using the technique of discharge-flow mass spectrometry with low-energy (12-eV) electron-impact ionization and collision-free sampling. Cl and CH{sub 3} were generated rapidly and simultaneously by reaction of F with HCl and CH{sub 4}, respectively. Fluorine atoms were produced by microwave discharge in an approximately 1% mixture of F{sub 2} in He. The decay of CH{sub 3} was monitored under pseudo-first-order conditions with the Cl-atom concentration in large excess over the CH{sub 3} concentration ([Cl]{sub 0}/[CH{sub 3}]{sub 0} = 9-67). Small corrections were made for both axial and radial diffusion and minor secondary chemistry. The rate coefficient was found to be in the falloff regime over the range of pressures studied. For example, at T = 202 K, the rate coefficient increases from 8.4 x 10{sup -12} at P = 0.30 Torr He to 1.8 x 10{sup -11} at P = 2.00 Torr He, both in units of cm{sup 3} molecule{sup -1} s{sup -1}. A combination of ab initio quantum chemistry, variational transition-state theory, and master-equation simulations was employed in developing a theoretical model for the temperature and pressure dependence of the rate coefficient. Reasonable empirical representations of energy transfer and of the effect of spin-orbit interactions yield a temperature- and pressure-dependent rate coefficient that is in excellent agreement with the present experimental results. The high-pressure limiting rate coefficient from the RRKM calculations is k{sub 2} = 6.0 x 10{sup -11} cm{sup 3} molecule{sup -1} s{sup -1}, independent of temperature in the range from 200 to 300 K.
NASA Astrophysics Data System (ADS)
Shizgal, Bernie D.
2016-08-01
Nonclassical quadratures based on a new set of half-range polynomials, Tn(x) , orthogonal with respect to w(x) =e - x - b /√{ x } for x ∈ [ 0 , ∞) are employed in the efficient calculation of the nuclear fusion reaction rate coefficients from cross section data. The parameter b = B /√{kB T } in the weight function is temperature dependent and B is the Gamow factor. The polynomials Tn(x) satisfy a three term recurrence relation defined by two sets of recurrence coefficients, αn and βn. These recurrence coefficients define in turn the tridiagonal Jacobi matrix whose eigenvalues are the quadrature points and the weights are calculated from the first components of the eigenfunctions. For nonresonant nuclear reactions for which the astrophysical function can be expressed as a lower order polynomial in the relative energy, the convergence of the thermal average of the reactive cross section with this nonclassical quadrature is extremely rapid requiring in many cases 2-4 quadrature points. The results are compared with other libraries of nuclear reaction rate coefficient data reported in the literature.
NASA Technical Reports Server (NTRS)
Fang, Z.; Kwong, Victor H. S.
1997-01-01
The charge transfer rate coefficient for the reaction N(2+)(2p(sup 2)P(sup 0)) + He yields products is measured by recording the time dependence of the N(2+) ions stored in an ion trap. A cylindrical radio-frequency ion trap was used to store N(2+) ions produced by laser ablation of a solid titanium nitride target. The decay of the ion signals was analyzed by single exponential least-squares fits to the data. The measured rate coefficient is 8.67(0.76) x 10(exp -11)sq cm/s. The N(2+) ions were at a mean energy of 2.7 eV while He gas was at room temperature, corresponding to an equivalent temperature of 3.9 x 10(exp 3) K. The measured value is in good agreement with a recent calculation.
NASA Astrophysics Data System (ADS)
Buchachenko, A. A.; Kroupnov, A. A.; Kovalev, V. L.
2015-08-01
Elementary stage rate coefficients of the full system of kinetic equations describing heterogeneous catalytic recombination of the dissociated air on the surfaces of thermal protective ceramic coatings of β-cristobalite and α-Al2O3 are determined using the quantum-mechanical calculations within the framework of cluster models and literature data. Both the impact and associative recombination processes of adsorbed oxygen and nitrogen atoms are taken into account.
Rate coefficient for H + O2 + M = HO2 + M evaluated from shock tube measurements of induction times
NASA Technical Reports Server (NTRS)
Slack, M. W.
1977-01-01
Shock tube experiments measured hydrogen-air induction times near the second explosion limit. By matching these experimental results with numerically predicted induction times, the rate coefficient for the reaction H + O2 + M = HO2 + M was evaluated as k-sub 4,N2 = 3.3 (plus or minus .6) x 10 to the 15 cm to the 6th/sq mole/s.
Absolute rate of the reaction of atomic hydrogen with ethylene from 198 to 320 K at high pressure
NASA Technical Reports Server (NTRS)
Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.
1978-01-01
The rate constant for the H+C2H4 reaction has been measured as a function of temperature. Experiments were performed with high pressures of Ar heat bath gas at seven temperatures from 198 to 320 K with the flash photolysis-resonance fluorescence (FP-RF) technique. Pressures were chosen so as to isolate the addition rate constant k1. The results are well represented by an Arrhenius expression. The results are compared with other studies and are theoretically discussed.
Absolute rate of the reaction of Cl(p-2) with molecular hydrogen from 200 - 500 K
NASA Technical Reports Server (NTRS)
Whytock, D. A.; Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.
1976-01-01
Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using the flash photolysis-resonance fluorescence technique. The results are compared with previous work and are discussed with particular reference to the equilibrium constant for the reaction and to relative rate data for chlorine atom reactions. Theoretical calculations, using the BEBO method with tunneling, give excellent agreement with experiment.
NASA Astrophysics Data System (ADS)
Phillips, Alfred, Jr.
Summ means the entirety of the multiverse. It seems clear, from the inflation theories of A. Guth and others, that the creation of many universes is plausible. We argue that Absolute cosmological ideas, not unlike those of I. Newton, may be consistent with dynamic multiverse creations. As suggested in W. Heisenberg's uncertainty principle, and with the Anthropic Principle defended by S. Hawking, et al., human consciousness, buttressed by findings of neuroscience, may have to be considered in our models. Predictability, as A. Einstein realized with Invariants and General Relativity, may be required for new ideas to be part of physics. We present here a two postulate model geared to an Absolute Summ. The seedbed of this work is part of Akhnaton's philosophy (see S. Freud, Moses and Monotheism). Most important, however, is that the structure of human consciousness, manifest in Kenya's Rift Valley 200,000 years ago as Homo sapiens, who were the culmination of the six million year co-creation process of Hominins and Nature in Africa, allows us to do the physics that we do. .
NASA Astrophysics Data System (ADS)
Narayanan, S.; Mohan Kumar, M.; Hassanizadeh, S. M.; Raoof, A.
2014-12-01
The colloid deposition behavior observed at the Darcy scale represents an average of the processes occurring at the pore scale. Hence, a better understanding of the processes occurring at the Darcy scale can be obtained by studying colloid transport at the pore-scale and then upscaling the results. In this study, we have developed a mathematical model to simulate the transport of colloids in a cylindrical pore by considering various processes such as advection, diffusion, colloid-soil surface interactions and hydrodynamic wall effects. The pore space is divided into three different regions, namely, the bulk, diffusion and potential regions, based on the dominant processes acting in each of these regions. In the bulk region, colloid transport is governed by advection and diffusion; whereas in the diffusion region, colloid mobility due to diffusion is retarded by hydrodynamic wall effects. Colloid-solid interaction forces dominate the transport in the potential region where colloid deposition occurs and are calculated using DLVO theory. The expressions for mass transfer rate coefficients between the diffusion and potential regions have been derived for different DLVO energy profiles. These are incorporated in the pore-scale equations in the form of a boundary condition at the diffusion-potential region interface. The model results are used to obtain the colloid breakthrough curve at the end of a long pore, and then it is fitted with 1D advection-dispersion-adsorption model so as to determine the averaged attachment and detachment rate coefficients at the scale of a single pore. A sensitivity analysis of the model to six pore-scale parameters (colloid and wall surface potentials, solution ionic strength, average pore-water velocity, colloid radius, and pore radius) is carried out so as to find the relation between the averaged deposition rate coefficients at pore scale vs the pore-scale parameters. We found an hyper exponential relation between the colloid attachment
Absolute rate constant of the reaction OH + H2O2 yields HO2 + H2O from 245 to 423 K
NASA Technical Reports Server (NTRS)
Keyser, L. F.
1980-01-01
The absolute rate constant of the reaction between the hydroxyl radical and hydrogen peroxide was measured by using the discharge-flow resonance fluorescence technique at total pressure between 1 and 4 torr. At 298 K the result is (1.64 + or - 0.32) x 10 to the -12th cu cm/molecule s. The observed rate constant is independent of pressure, surface-to-volume ratio, the addition of vibrational quenchers, and the source of OH. The temperature dependence has also been determined between 245 and 423 K; the resulting Arrhenius expression is k cu cm/molecule s is equal to (2.51 + or - 0.6) x 10 to the -12th exp(-126 + or - 76/T).
NASA Astrophysics Data System (ADS)
Glover, Simon C. O.
2015-11-01
We investigate how uncertainties in the chemical and cooling rate coefficients relevant for a metal-free gas influence our ability to determine the critical ultraviolet field strength required to suppress H2 cooling in high-redshift atomic cooling haloes. The suppression of H2 cooling is a necessary prerequisite for the gas to undergo direct collapse and form an intermediate mass black hole. These black holes can then act as seeds for the growth of the supermassive black holes (SMBHs) observed at redshifts z ˜ 6. The viability of this model for SMBH formation depends on the critical ultraviolet field strength, Jcrit: if this is too large, then too few seeds will form to explain the observed number density of SMBHs. We show in this paper that there are five key chemical reactions whose rate coefficients are uncertain enough to significantly affect Jcrit. The most important of these is the collisional ionization of hydrogen by collisions with other hydrogen atoms, as the rate for this process is very poorly constrained at the low energies relevant for direct collapse. The total uncertainty introduced into Jcrit by this and the other four reactions could in the worst case approach a factor of five. We also show that the use of outdated or inappropriate values for the rates of some chemical reactions in previous studies of the direct collapse mechanism may have significantly affected the values of Jcrit determined by these studies.
Absolute rate constants for O + NO + M /= He, Ne, Ar, Kr/ yields NO2 + M from 217-500 K
NASA Technical Reports Server (NTRS)
Michael, J. V.; Payne, W. A.; Whytock, D. A.
1976-01-01
Rate constants for the reaction O + NO + M yields NO2 + M have been obtained at temperatures from 217-500 K in four different rare gases by a method combining flash photolysis with time resolved detection of O(3-P) by resonance fluorescence. The measured rate constants in Arrhenius form are (10.8 plus or minus 1.2) x 10 to the -33rd exp(1040 plus or minus 60/1.987 T) for helium; (9.01 plus or minus 1.16) x 10 to the -33rd exp(1180 plus or minus 70/1.987 T) for argon; (9.33 plus or minus 1.10) x 10 to the -33rd exp(1030 plus or minus 60/1.987 T) for neon; and (9.52 plus or minus 1.10) x 10 to the -33rd exp(1140 plus or minus 70/1.987 T) for krypton in units of cm to the 6th/sq molecule/s.
Yao, Kangning; Chi, Yong; Wang, Fei; Yan, Jianhua; Ni, Mingjiang; Cen, Kefa
2016-01-01
A commonly used aeration device at present has the disadvantages of low mass transfer rate because the generated bubbles are several millimeters in diameter which are much bigger than microbubbles. Therefore, the effect of a microbubble on gas-liquid mass transfer and wastewater treatment process was investigated. To evaluate the effect of each bubble type, the volumetric mass transfer coefficients for microbubbles and conventional bubbles were determined. The volumetric mass transfer coefficient was 0.02905 s(-1) and 0.02191 s(-1) at a gas flow rate of 0.67 L min(-1) in tap water for microbubbles and conventional bubbles, respectively. The degradation rate of simulated municipal wastewater was also investigated, using aerobic activated sludge and ozone. Compared with the conventional bubble generator, the chemical oxygen demand (COD) removal rate was 2.04, 5.9, 3.26 times higher than those of the conventional bubble contactor at the same initial COD concentration of COD 200 mg L(-1), 400 mg L(-1), and 600 mg L(-1), while aerobic activated sludge was used. For the ozonation process, the rate of COD removal using microbubble generator was 2.38, 2.51, 2.89 times of those of the conventional bubble generator. Based on the results, the effect of initial COD concentration on the specific COD degradation rate were discussed in different systems. Thus, the results revealed that microbubbles could enhance mass transfer in wastewater treatment and be an effective method to improve the degradation of wastewater. PMID:27120652
NASA Astrophysics Data System (ADS)
Portman, John J.
2003-02-01
Intrachain contact formation rates, fundamental to the dynamics of biopolymer self-organization such as protein folding, can be monitored in the laboratory through fluorescence quenching measurements. The common approximations for the intrachain contact rate given by the theory of Szabo, Schulten, and Schulten (SSS) [J. Chem. Phys. 72, 4350 (1980)] and Wilemski-Fixman (WF) [J. Chem. Phys. 60, 878 (1973)] are shown to be complementary variational bounds: The SSS and WF approximations are lower and upper bounds, respectively, on the mean first contact times. As reported in the literature, the SSS approximation requires an effective diffusion coefficient 10 to 100 times smaller than expected to fit experimentally measured quenching rates. An all atom molecular dynamics simulation of an eleven residue peptide sequence in explicit water is analyzed to investigate the source of this surprising parameter value. The simulated diffusion limited contact time is ≈6 ns for a reaction radius of 4 Å for solvent viscosity corresponding to that of water at 293 K and 1 atm (η=1.0 cP). In analytical work, the polymer is typically modeled by a Gaussian chain of effective monomers. Compared to Gaussian dynamics, the simulated end-to-end distance autocorrelation has a much slower relaxation. The long time behavior of the distance autocorrelation function can be approximated by a Gaussian model in which the monomer diffusion coefficient D0 is reduced to D0/6. This value of the diffusion coefficient brings the mean end-to-end contact time from analytical approximations and simulation into agreement in the sense that the SSS and WF approximations bracket the simulated mean first contact time.
Lu, Chih-Wei; Chou, Shen-Long; Lee, Yuan-Pern; Xu, Shucheng; Xu, Z F; Lin, M C
2005-06-22
Rate coefficients of the reaction O((3)P) + CH(3)OH in the temperature range of 835-1777 K were determined using a diaphragmless shock tube. O atoms were generated by photolysis of SO(2) with a KrF excimer laser at 248 nm or an ArF excimer laser at 193 nm; their concentrations were monitored via atomic resonance absorption excited by emission from a microwave-discharged mixture of O(2) and He. The rate coefficients determined for the temperature range can be represented by the Arrhenius equation, k(T) = (2.29 +/- 0.18) x 10(-10) exp[-(4210 +/- 100)T] cm(3) molecule(-1) s(-1); unless otherwise noted, all the listed errors represent one standard deviation in fitting. Combination of these and previous data at lower temperature shows a non-Arrhenius behavior described as the three-parameter equation, k(T) = (2.74 +/- 0.07) x 10(-18)T(2.25 +/- 0.13) exp[-(1500 +/- 90)T] cm(3)molecule(-1) s(-1). Theoretical calculations at the Becke-3-Lee-Yang-Parr (B3LYP)6-311 + G(3df,2p) level locate three transition states. Based on the energies computed with coupled clusters singles, doubles (triples) [CCSD(T)]/6-311 + G(3df,2p)B3LYP6-311 + G(3df,2p), the rate coefficients predicted with canonical variational transition state theory with small curvature tunneling corrections agree satisfactorily with the experimental observations. The branching ratios of two accessible reaction channels forming OH + CH(2)OH (1a) and OH + CH(3)O (1b) are predicted to vary strongly with temperature. At 300 K, reaction (1a) dominates, whereas reaction (1b) becomes more important than reaction (1a) above 1700 K. PMID:16035764
NASA Astrophysics Data System (ADS)
Lhotka, C.; Reimond, S.; Souchay, J.; Baur, O.
2016-02-01
The aim of this study is first to determine the gravity field of the comet 67P/Churyumov-Gerasimenko and second to derive the solar component of the precession rate and nutation coefficients of the spin-axis of the comet nucleus, i.e. without the direct, usually larger, effect of outgassing. The gravity field and related moments of inertia are obtained from two polyhedra, which are provided by the Optical, Spectroscopic, and Infrared Remote Imaging System (OSIRIS) and NAVigation CAMera (NAVCAM) experiments on Rosetta, and are based on the assumption of uniform density for the comet nucleus. We also calculate the forced precession rate as well as the nutation coefficients on the basis of Kinoshita's theory of rotation of the rigid Earth and adapted it to be able to indirectly include the effect of outgassing on the rotational parameters. The second degree denormalized Stokes coefficients of comet 67P/C-G turn out to be (bracketed numbers refer to second shape model) C20 ≃ -6.74 [-7.93] × 10-2, C22 ≃ 2.60 [2.71] × 10-2, consistent with normalized principal moments of inertia A/MR2 ≃ 0.13 [0.11], B/MR2 ≃ 0.23 [0.22], with polar moment c = C/MR2 ≃ 0.25, depending on the choice of the polyhedron model. The obliquity between the rotation axis and the mean orbit normal is ε ≃ 52°, and the precession rate only due to solar torques becomes dot{ψ }in [20,30] arcsec yr^{-1}. Oscillations in longitude caused by the gravitational pull of the Sun turn out to be of the order of Δψ ≃ 1 arcmin, and oscillations in obliquity can be estimated to be of the order of Δε ≃ 0.5 arcmin.
Anders, R.; Chrysikopoulos, C.V.
2006-01-01
Static and dynamic batch experiments were conducted to study the effects of temperature and the presence of sand on the inactivation of bacteriophage MS2 and PRD1. The experimental data suggested that the inactivation process can be satisfactorily represented by a pseudo-first-order expression with time-dependent rate coefficients. The time-dependent rate coefficients were used to determine pertinent thermodynamic properties required for the analysis of the molecular processes involved in the inactivation of each bacteriophage. A combination of high temperature and the presence of sand appears to produce the greatest disruption to the surrounding protein coat of MS2. However, the lower activation energies for PRD1 indicate a weaker dependence of the inactivation rate on temperature. Instead, the presence of air-liquid and air-solid interfaces appears to produce the greatest damage to specific viral components that are related to infection. These results indicate the importance of using thermodynamic parameters based on the time-dependent inactivation model to better predict the inactivation of viruses in groundwater. ?? 2006 American Chemical Society.
Drexler, J.Z.; Anderson, F.E.; Snyder, R.L.
2008-01-01
The surface renewal method was used to estimate evapotranspiration (ET) for a restored marsh on Twitchell Island in the Sacramento-San Joaquin Delta, California, USA. ET estimates for the marsh, together with reference ET measurements from a nearby climate station, were used to determine crop coefficients over a 3-year period during the growing season. The mean ET rate for the study period was 6 mm day-1, which is high compared with other marshes with similar vegetation. High ET rates at the marsh may be due to the windy, semi-arid Mediterranean climate of the region, and the permanently flooded nature of the marsh, which results in very low surface resistance of the vegetation. Crop coefficient (Kc) values for the marsh ranged from 0.73 to 1.18. The mean Kc value over the entire study period was 0-95. The daily Kc values for any given month varied from year to year, and the standard deviation of daily Kc values varied between months. Although several climate variables were undoubtedly responsible for this variation, our analysis revealed that wind direction and the temperature of standing water in the wetland were of particular importance in determining ET rates and Kc values.
Miller, James A; Klippenstein, Stephen J
2013-04-01
In this article we discuss at length the determination of phenomenological rate coefficients from the solution to a time-dependent, multiple-well master equation. Both conservative and non-conservative formulations are considered. The emphasis is placed on how to handle the situation when a CSE (chemically significant eigenvalue of the transition matrix) merges with the quasi-continuum of IEREs (internal energy relaxation eigenvalues), indicating that one or more chemical reactions begin to take place on vibrational-rotational relaxation time scales. The methodology is illustrated with four examples. PMID:23435763
NASA Astrophysics Data System (ADS)
Yaseen, Mohammad A.; Srinivasan, Vivek J.; Sakadžić, Sava; Vinogradov, Sergei A.; Boas, David A.
2010-02-01
Measuring oxygen delivery in brain tissue is important for identifying the pathophysiological changes associated with brain injury and various diseases such as cancer, stroke, and Alzheimer's disease. We have developed a multi-modal imaging system for minimally invasive measurement of cerebral oxygenation and blood flow in small animals with high spatial resolution. The system allows for simultaneous measurement of blood flow using Fourier-domain optical coherence tomography, and oxygen partial pressure (pO2) using either confocal or multiphoton phosphorescence lifetime imaging with exogenous porphyrin-based dyes sensitive to dissolved oxygen. Here we present the changes in pO2 and blood flow in superficial cortical vessels of Sprague Dawley rats in response to conditions such as hypoxia, hyperoxia, and functional stimulation. pO2 measurements display considerable heterogeneity over distances that cannot be resolved with more widely used oxygen-monitoring techniques such as BOLD-fMRI. Large increases in blood flow are observed in response to functional stimulation and hypoxia. Our system allows for quantification of cerebral metabolic rate of oxygen (CMRO2) with high spatial resolution, providing a better understanding of metabolic dynamics during functional stimulation and under various neuropathologies. Ultimately, better insight into the underlying mechanisms of neuropathologies will facilitate the development of improved therapeutic strategies to minimize damage to brain tissue.
Pressure dependence of the absolute rate constant for the reaction Cl + C2H2 from 210-361 K
NASA Technical Reports Server (NTRS)
Brunning, J.; Stief, L. J.
1985-01-01
In recent years, considerable attention has been given to the role of chlorine compounds in the catalytic destruction of stratospheric ozone. However, while some reactions have been studied extensively, the kinetic data for the reaction of Cl with C2H2 is sparse with only three known determinations of the rate constant k3. The reactions involved are Cl + C2H2 yields reversibly ClC2H2(asterisk) (3a) and ClC2H2(asterisk) + M yields ClC2H2 + M (3b). In the present study, flash photolysis coupled with chlorine atomic resonance fluorescence have been employed to determine the pressure and temperature dependence of k3 with the third body M = Ar. Room temperature values are also reported for M = N2. The pressure dependence observed in the experiments confirms the expectation that the reaction involves addition of Cl to the unsaturated C2H2 molecule followed by collisional stabilization of the resulting adduct radical.
NASA Astrophysics Data System (ADS)
Coppage, Steven Danforth
We report 644 absolute level-to-level inelastic and reactive constants for the L7i*2 A1S+u (nui, ji) + 7Li → L7i*2 A1S+u (nu', j') + 7Li system with initial molecular quantum numbers nui = 2 and ji = 3, 11, and 19. We collected 87 rate constants for rotationally inelastic and vibrationally elastic collisions, 281 rate constants for vibrationally inelastic collisions, and 276 constants for exchange reactions with final vibrational levels from nu f = 0 to nuf = 3. Inelastic collisions are characterized by even changes in rotational quantum number, j , and exchange reactions are identified by odd Deltaj. Level-to-level rate constants for even Deltaj inelastic collisions show distributions similar to those in rare gas collisions with the excited Li2 molecule. The ECS (energy corrected sudden) scaling law of DePristo, et al., fit the vibrationally elastic data well. Reactive rate constant results are characterized by a statistical distribution for Deltanu of 0, -1, and -2 at a substantially reduced effective temperature consistent with a kinematic model proposed by Picconatto et al. Fitting quasiclassical trajectory studies to the data using a modified LEPS potential surface provide first insights into the parameters of the excited-state Li3* three-body potential.
NASA Technical Reports Server (NTRS)
Dateo, Christopher E.; Walch, Stephen P.
2002-01-01
As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.
NASA Astrophysics Data System (ADS)
Ivanov, Konstantin L.; Lukzen, Nikita N.; Doktorov, Alexander B.
2016-08-01
Time dependence of the rate coefficients of sterically specific reactions is analyzed theoretically. Generally, such reactions exhibit a non-trivial dependence of their rate constant on the steric factor, f < 1, which is defined as the fraction of reactive surface area. Notably, the rate constant of a diffusion-controlled reaction is proportional not to f but, counter-intuitively, to √{ f } due to partial averaging of the reaction anisotropy by translational diffusion. Here we demonstrate that the effective steric factor of a diffusion-influenced reaction is strongly time-dependent, increasing from f to √{ f } . When reactants have several active sites, these sites "interfere" each other in the sense that the rate constant depends on their relative positions. We demonstrate that such an interference effect is strongly time-dependent as well: it is absent at t = 0 but builds up with time. We argue that the outlined effects are also of importance for calculating the fluorescence quenching rate constants.
Collisional quenching reaction rate coefficients of N2 (A3Σu+) by C2F6 and C3F8
NASA Astrophysics Data System (ADS)
Suzuki, Susumu; Kuboaki, Masaru; Itoh, Haruo
2015-09-01
The collisional quenching reaction rate coefficient of N2 (A3Σu+) by various air pollutant gases were determined from the measurement of the effective lifetime of N2 (A3Σu+) in pure N2 (5-nine) with a small amount of air pollutant gases as an admixture. Derivation of the rate coefficient was performed the waveform analysis of the transient ionization current after turning off the UV light in the Townsend discharge. In this paper, we report that the obtained collisional quenching reaction rate coefficients of N2 (A3Σu+) by C2F6 and C3F8 are (2.3 +/- 1.8) × 10-15 cm3/s and (1.6 +/- 0.8) × 10-14 cm3/s, respectively. Furthermore, we investigate the relationship between the rate coefficient and the mass number of their quenching molecular gases. Firstly, it is confirmed that the rate coefficient take large value with an increase in the mass number of the quenching gases. Secondly, if H atom is included in the gas molecules such as CH4, C2F6 and C3F8 the rate coefficient take large value, but if the molecules including F atom such as C2F6 and C3F8 instead of H atom in this study, more smaller values of the collisional quenching reaction rate coefficient are observed.
Scheibe, Timothy D.; Dong, Hailiang; Xie, YuLong
2007-06-01
It has been widely observed in field experiments that the apparent rate of bacterial attachment, particularly as parameterized by the collision efficiency in filtration-based models, decreases with transport distance (i.e., exhibits scale-dependency). This effect has previously been attributed to microbial heterogeneity; that is, variability in cell-surface properties within a single monoclonal population. We demonstrate that this effect could also be interpreted as a field-scale manifestation of local-scale correlation between physical heterogeneity (hydraulic conductivity variability) and reaction heterogeneity (attachment rate coefficient variability). A field-scale model of bacterial transport developed for the South Oyster field research site located near Oyster, Virginia, and observations from field experiments performed at that site, are used as the basis for this study. Three-dimensional Monte Carlo simulations of bacterial transport were performed under four alternative scenarios: 1) homogeneous hydraulic conductivity (K) and attachment rate coefficient (Kf), 2) heterogeneous K, homogeneous Kf, 3) heterogeneous K and Kf with local correlation based on empirical and theoretical relationships, and 4) heterogeneous K and Kf without local correlation. The results of the 3D simulations were analyzed using 1D model approximations following conventional methods of field data analysis. An apparent decrease with transport distance of effective collision efficiency was observed only in the case where the local properties were both heterogeneous and correlated. This effect was observed despite the fact that the local collision efficiency was specified as a constant in the 3D model, and can therefore be interpreted as a scale effect associated with the local correlated heterogeneity as manifested at the field scale.
NASA Astrophysics Data System (ADS)
Gibilisco, Rodrigo G.; Santiago, Ana N.; Teruel, Mariano A.
2013-10-01
The kinetics of the reactions of OH radicals with three C6 unsaturated alcohols at 298 K and atmospheric pressure were investigated using solid phase microextraction (SPME) with GC-FID detection of organic compounds. Rate coefficients (in cm3 molecule-1 s-1) of k1(OH + (E)-CH2OHCHdbnd CH(CH2)2CH3) = (1.0 ± 0.3) × 10-10, k2(OH + (E)-CH2OHCH2CHdbnd CHCH2CH3) = (1.2 ± 0.2) × 10-10 and k3(OH + (Z)-CH2OHCH2CHdbnd CHCH2CH3) = (1.4 ± 0.3) × 10-10 were obtained by the relative rate method using methyl methacrylate and (E)-2-buten-1-ol as references. Rate coefficients were compared with previous determinations and reactivity trends were developed and rationalized in terms of the effect and position of substituents in the unsaturated alcohol. A correlation between the reactivity of unsaturated alcohols toward OH radicals and the energy of the HOMO of the unsaturated alcohol is presented. Additionally, product identification under atmospheric conditions was performed for the first time for these unsaturated C6 alcohols by the GC-MS technique. Butanal was observed as the main degradation product of OH with (E)-2-hexen-1-ol, in accordance with the decomposition of the 2,3-hydroxyalcoxy radicals formed. On the basis of our kinetic measurements, tropospheric lifetimes of the studied unsaturated compounds are estimated.
Low-Temperature Rate Coefficients of C2H with CH4 and CD4 from 154 to 359 K
NASA Technical Reports Server (NTRS)
Opansky, Brian J.; Leone, Stephen R.
1996-01-01
Rate coefficients for the reaction C2H + CH4 yields C2H2 + CH3 and C2H + CD4 yields C2HD + CD3 are measured over the temperature range 154-359 K using transient infrared laser absorption spectroscopy. Ethynyl radicals are produced by pulsed laser photolysis of C2H2 in a variable temperature flow cell, and a tunable color center laser probes the transient removal of C2H (Chi(exp 2) Sigma(+) (0,0,0)) in absorption. The rate coefficients for the reactions of C2H with CH4 and CD4 both show a positive temperature dependence over the range 154-359 K, which can be expressed as k(sub CH4) = (1.2 +/- 0.1) x 10(exp -11) exp((-491 +/- 12)/T) and k(sub CD4) = (8.7 +/- 1.8) x 10(exp -12) exp((-650 +/- 61)/T) cm(exp 3) molecule(exp -1) s(exp -1), respectively. The reaction of C2H + CH4 exhibits a significant kinetic isotope effect at 300 K of k(sub CH4)/k(sub CD4) = 2.5 +/- 0.2. Temperature dependent rate constants for C2H + C2H2 were also remeasured over an increased temperature range from 143 to 359 K and found to show a slight negative temperature dependence, which can be expressed as k(sub C2H2) = 8.6 x 10(exp -16) T(exp 1.8) exp((474 +/- 90)/T) cm(exp 3) molecule(exp -1) s(exp -1).
NASA Technical Reports Server (NTRS)
Gray, Vernon H.
1958-01-01
An empirical relation has been obtained by which the change in drag coefficient caused by ice formations on an unswept NACA 65AO04 airfoil section can be determined from the following icing and operating conditions: icing time, airspeed, air total temperature, liquid-water content, cloud droplet impingement efficiencies, airfoil chord length, and angles of attack. The correlation was obtained by use of measured ice heights and ice angles. These measurements were obtained from a variety of ice formations, which were carefully photographed, cross-sectioned, and weighed. Ice weights increased at a constant rate with icing time in a rime icing condition and at progressively increasing rates in glaze icing conditions. Initial rates of ice collection agreed reasonably well with values predicted from droplet impingement data. Experimental droplet impingement rates obtained on this airfoil section agreed with previous theoretical calculations for angles of attack of 40 or less. Disagreement at higher angles of attack was attributed to flow separation from the upper surface of the experimental airfoil model.
Determination of the Rate Coefficients of the SO2 plus O plus M yields SO3 plus M Reaction
NASA Technical Reports Server (NTRS)
Hwang, S. M.; Cooke, J. A.; De Witt, K. J.; Rabinowitz, M. J.
2010-01-01
Rate coefficients of the title reaction R(sub 31) (SO2 +O+M yields SO3 +M) and R(sub 56) (SO2 + HO2 yields SO3 +OH), important in the conversion of S(IV) to S(VI),were obtained at T =970-1150 K and rho (sub ave) = 16.2 micro mol/cubic cm behind reflected shock waves by a perturbation method. Shock-heated H2/ O2/Ar mixtures were perturbed by adding small amounts of SO2 (1%, 2%, and 3%) and the OH temporal profiles were then measured using laser absorption spectroscopy. Reaction rate coefficients were elucidated by matching the characteristic reaction times acquired from the individual experimental absorption profiles via simultaneous optimization of k(sub 31) and k(sub 56) values in the reaction modeling (for satisfactory matches to the observed characteristic times, it was necessary to take into account R(sub 56)). In the experimental conditions of this study, R(sub 31) is in the low-pressure limit. The rate coefficient expressions fitted using the combined data of this study and the previous experimental results are k(sub 31,0)/[Ar] = 2.9 10(exp 35) T(exp ?6.0) exp(?4780 K/T ) + 6.1 10(exp 24) T(exp ?3.0) exp(?1980 K/T ) cm(sup 6) mol(exp ?2)/ s at T = 300-2500 K; k(sub 56) = 1.36 10(exp 11) exp(?3420 K/T ) cm(exp 3)/mol/s at T = 970-1150 K. Computer simulations of typical aircraft engine environments, using the reaction mechanism with the above k(sub 31,0) and k(sub 56) expressions, gave the maximum S(IV) to S(VI) conversion yield of ca. 3.5% and 2.5% for the constant density and constant pressure flow condition, respectively. Moreover, maximum conversions occur at rather higher temperatures (?1200 K) than that where the maximum k(sub 31,0) value is located (approximately 800 K). This is because the conversion yield is dependent upon not only the k(sup 31,0) and k(sup 56) values (production flux) but also the availability of H, O, and HO2 in the system (consumption flux).
Cross sections and rate coefficients for inner-shell excitation of Li-like ions with 6 < Z < 42
NASA Astrophysics Data System (ADS)
Safronova, U. I.; Safronova, M. S.; Kato, T.
1996-07-01
Excitation cross sections and rate coefficients by electron impact were calculated for the 1s22s-1s2s2p, 1s22s-1s2s2 and 1s22s-1s2p2 transitions of the Li-like ions (C IV, N V, O VI, Ne VIII, Mg X, Al XI, Si XII, S XIV, Ar XVI, Ca XVIII, Ti XX, Fe XXIV, Ni XXVI, Zn XXVIII, Ge XXX, Se XXXII, Kr XXXIV and Mo XXXX) in the Coulomb-Born approximation with exchange including relativistic effects and configuration interaction. Level energies, mixing coefficients and transition wavelengths and probabilities were also computed. Calculations performed by the 1/Z perturbation theory and Coulomb-Born approximation are compared with the R-matrix method and the distorted-wave approximation were Z is the nuclear charge. Formulae obtained for the angular factors of n-electron atomic system allow one to generalize this method to an arbitrary system of highly charged ions.
Coppola, C. M.; Longo, S.; D'Introno, R.; Galli, D.; Tennyson, J.
2012-03-01
Energy exchange processes play a crucial role in the early universe, affecting the thermal balance and the dynamical evolution of the primordial gas. In the present work we focus on the consequences of a non-thermal distribution of the level populations of H{sub 2}: first, we determine the excitation temperatures of vibrational transitions and the non-equilibrium heat transfer; second, we compare the modifications to chemical reaction rate coefficients with respect to the values obtained assuming local thermodynamic equilibrium; and third, we compute the spectral distortions to the cosmic background radiation generated by the formation of H{sub 2} in vibrationally excited levels. We conclude that non-equilibrium processes cannot be ignored in cosmological simulations of the evolution of baryons, although their observational signatures remain below current limits of detection. New fits to the equilibrium and non-equilibrium heat transfer functions are provided.
NASA Astrophysics Data System (ADS)
Feofilov, A.; Kutepov, A.; She, C.; Smith, A. K.; Pesnell, W. D.; Goldberg, R. A.
2009-12-01
Among the processes governing the energy balance in the mesosphere and lower thermosphere (MLT), the quenching of CO2(ν2) vibrational levels in collisions with oxygen atoms plays an important role. However, neither the rate coefficient of this process (k(CO2-O)) nor the atomic oxygen concentrations ([O]) in the MLT are well known. The discrepancy between k(CO2-O) measured in the lab and retrieved from atmospheric measurements is of about factor of 2.5. At the same time, the discrepancy between [O] in the MLT measured by different instruments is of the same order of magnitude. In this work we combine temperature data from a ground based lidar with limb radiances from a satellite infrared radiometer to estimate k(CO2-O). We used the night- and daytime temperatures between 80 and 110 km measured by the Colorado State University narrow-band sodium (Na) lidar located at Fort Collins, Colorado (41N, 255E) as ground truth of the SABER/TIMED nearly simultaneous (±10 minutes ) and common volume (within ±1 degree in latitude, ±2 degrees in longitude) observations. We used ALI-ARMS non-LTE research code designed to calculate the non-equilibrium radiance in planetary atmospheres to retrieve the product of k(CO2-O) x [O] from 15 μm CO2 limb radiance measured by SABER. The values retrieved for all overlapping measurements were then used to estimate the k(CO2-O) rate coefficient and its possible variation range by utilizing the [O] values measured by the SABER and other instruments.
NASA Astrophysics Data System (ADS)
Sallaska, Anne L.
2010-11-01
Hydrodynamic simulations of classical novae on ONe white dwarfs predict substantial production of 22Na. Observation of 22Na decay should be correlated with the corresponding nova because the half life of 22Na is only 2.6 years. The 1275-keV gamma ray from the beta decay of 22Na is, therefore, an excellent diagnostic for the nova phenomenon and a long-sought target of gamma-ray telescopes. Nova simulations determine the maximum 22Na-detection distance to be < 1 kpc for the INTEGRAL spectrometer SPI, consistent with its non-observation to date. However, model estimates are strongly dependent on the thermonuclear rate of the 22Na(p, gamma)23Mg reaction, which is the main destruction mechanism of 22Na in novae. The 22Na(p,gamma)23Mg rate is expected to be dominated by narrow, isolated resonances with Ep < 300 key. The currently employed rate is based on a single set of absolute resonance-strength measurements with Ep ≥ 290 keV, and one relative measurement of resonances with Ep ≥ 214 keV. Recently, a new level has been found in 23Mg which would correspond to a resonance at Ep = 198 keV that might dominate the reaction rate at nova temperatures. We have measured the 22Na(p, gamma) 23Mg resonance strengths directly and absolutely, in addition to resonance energies and branches. Proton beams were produced at the University of Washington and delivered to a specially designed beam line that included rastering and cold vacuum protection of the 22Na-implanted targets (fabricated at TRIUMF-ISAC). Two high-purity germanium detectors were employed and surrounded by anticoincidence shields to reduce cosmic backgrounds. Measurements were made on known 22Na+p resonances, which we observed at laboratory energies Ep = 213, 288, 454, 610 keV and on proposed resonances at Ep = 198, 209, and 232 key. The proposed resonances were not observed, and the upper limit placed on the 198-keV resonance strength indicates that the resonance at Ep = 213 keV still dominates the reaction rate
NASA Technical Reports Server (NTRS)
Reuter, Dennis C.; Sirota, J. Marcos
1993-01-01
Absolute intensities and foreign gas broadening coefficients of the 18(sub 0,18) from 18(sub 1,18) and 11(sub 1,10) from 11(sub 2,10) transitions in the nu(sub 7) band of C2H4 near 948/cm have been measured at a spectral resolution of approximately 5 x 10(exp -4)/cm using tunable diode laser spectrometry. Ar, He, N2, O2 were used as the broadening gases. In order to determine the temperature dependence of the broadening coefficient, data were obtained at temperatures ranging from 150 to 296 K. The absolute intensity of the 5(sub 0,5) from 5(sub 1,5) transition was also found at 296 K. A band strength of 330 +/- 10/sq cm/atm was obtained from weighted averages of the individual line intensities and a rigid asymmetric top calculation.
Pusateri, Elise N.; Morris, Heidi E.; Nelson, Eric M.; Ji, Wei
2015-08-04
Electromagnetic pulse (EMP) events produce low-energy conduction electrons from Compton electron or photoelectron ionizations with air. It is important to understand how conduction electrons interact with air in order to accurately predict EMP evolution and propagation. An electron swarm model can be used to monitor the time evolution of conduction electrons in an environment characterized by electric field and pressure. Here a swarm model is developed that is based on the coupled ordinary differential equations (ODEs) described by Higgins et al. (1973), hereinafter HLO. The ODEs characterize the swarm electric field, electron temperature, electron number density, and drift velocity. Importantmore » swarm parameters, the momentum transfer collision frequency, energy transfer collision frequency, and ionization rate, are calculated and compared to the previously reported fitted functions given in HLO. These swarm parameters are found using BOLSIG+, a two term Boltzmann solver developed by Hagelaar and Pitchford (2005), which utilizes updated cross sections from the LXcat website created by Pancheshnyi et al. (2012). We validate the swarm model by comparing to experimental effective ionization coefficient data in Dutton (1975) and drift velocity data in Ruiz-Vargas et al. (2010). In addition, we report on electron equilibrium temperatures and times for a uniform electric field of 1 StatV/cm for atmospheric heights from 0 to 40 km. We show that the equilibrium temperature and time are sensitive to the modifications in the collision frequencies and ionization rate based on the updated electron interaction cross sections.« less
NASA Astrophysics Data System (ADS)
Pusateri, Elise N.; Morris, Heidi E.; Nelson, Eric M.; Ji, Wei
2015-08-01
Electromagnetic pulse (EMP) events produce low-energy conduction electrons from Compton electron or photoelectron ionizations with air. It is important to understand how conduction electrons interact with air in order to accurately predict EMP evolution and propagation. An electron swarm model can be used to monitor the time evolution of conduction electrons in an environment characterized by electric field and pressure. Here a swarm model is developed that is based on the coupled ordinary differential equations (ODEs) described by Higgins et al. (1973), hereinafter HLO. The ODEs characterize the swarm electric field, electron temperature, electron number density, and drift velocity. Important swarm parameters, the momentum transfer collision frequency, energy transfer collision frequency, and ionization rate, are calculated and compared to the previously reported fitted functions given in HLO. These swarm parameters are found using BOLSIG+, a two term Boltzmann solver developed by Hagelaar and Pitchford (2005), which utilizes updated cross sections from the LXcat website created by Pancheshnyi et al. (2012). We validate the swarm model by comparing to experimental effective ionization coefficient data in Dutton (1975) and drift velocity data in Ruiz-Vargas et al. (2010). In addition, we report on electron equilibrium temperatures and times for a uniform electric field of 1 StatV/cm for atmospheric heights from 0 to 40 km. It is shown that the equilibrium temperature and time are sensitive to the modifications in the collision frequencies and ionization rate based on the updated electron interaction cross sections.
Kockler, Katrin B; Haehnel, Alexander P; Junkers, Thomas; Barner-Kowollik, Christopher
2016-01-01
Detailed knowledge of the polymerization mechanisms and kinetics of academically and industrially relevant monomers is mandatory for the precision synthesis of tailor-made polymers. The IUPAC-recommended pulsed-laser polymerization-size exclusion chromatography (PLP-SEC) approach is the method of choice for the determination of propagation rate coefficients and the associated Arrhenius parameters for free radical polymerization processes. With regard to specific monomer classes-such as acrylate-type monomers, which are very important from a materials point of view-high laser frequencies of up to 500 Hz are mandatory to prevent the formation of mid-chain radicals and the occurrence of chain-breaking events by chain transfer, if industrially relevant temperatures are to be reached and wide temperature ranges are to be explored (up to 70 °C). Herein the progress and state-of-the-art of high-frequency PLP-SEC with pulse repetition rates of 500 Hz is reported, with a critical collection of to-date investigated 500 Hz data as well as future perspectives for the field. PMID:26479174
NASA Astrophysics Data System (ADS)
Jambrina, P. G.; Lara, Manuel; Menéndez, M.; Launay, J.-M.; Aoiz, F. J.
2012-10-01
Cumulative reaction probabilities (CRPs) at various total angular momenta have been calculated for the barrierless reaction S(1D) + H2 → SH + H at total energies up to 1.2 eV using three different theoretical approaches: time-independent quantum mechanics (QM), quasiclassical trajectories (QCT), and statistical quasiclassical trajectories (SQCT). The calculations have been carried out on the widely used potential energy surface (PES) by Ho et al. [J. Chem. Phys. 116, 4124 (2002), 10.1063/1.1431280] as well as on the recent PES developed by Song et al. [J. Phys. Chem. A 113, 9213 (2009), 10.1021/jp903790h]. The results show that the differences between these two PES are relatively minor and mostly related to the different topologies of the well. In addition, the agreement between the three theoretical methodologies is good, even for the highest total angular momenta and energies. In particular, the good accordance between the CRPs obtained with dynamical methods (QM and QCT) and the statistical model (SQCT) indicates that the reaction can be considered statistical in the whole range of energies in contrast with the findings for other prototypical barrierless reactions. In addition, total CRPs and rate coefficients in the range of 20-1000 K have been calculated using the QCT and SQCT methods and have been found somewhat smaller than the experimental total removal rates of S(1D).
Pusateri, Elise N.; Morris, Heidi E.; Nelson, Eric M.; Ji, Wei
2015-08-04
Electromagnetic pulse (EMP) events produce low-energy conduction electrons from Compton electron or photoelectron ionizations with air. It is important to understand how conduction electrons interact with air in order to accurately predict EMP evolution and propagation. An electron swarm model can be used to monitor the time evolution of conduction electrons in an environment characterized by electric field and pressure. Here a swarm model is developed that is based on the coupled ordinary differential equations (ODEs) described by Higgins et al. (1973), hereinafter HLO. The ODEs characterize the swarm electric field, electron temperature, electron number density, and drift velocity. Important swarm parameters, the momentum transfer collision frequency, energy transfer collision frequency, and ionization rate, are calculated and compared to the previously reported fitted functions given in HLO. These swarm parameters are found using BOLSIG+, a two term Boltzmann solver developed by Hagelaar and Pitchford (2005), which utilizes updated cross sections from the LXcat website created by Pancheshnyi et al. (2012). We validate the swarm model by comparing to experimental effective ionization coefficient data in Dutton (1975) and drift velocity data in Ruiz-Vargas et al. (2010). In addition, we report on electron equilibrium temperatures and times for a uniform electric field of 1 StatV/cm for atmospheric heights from 0 to 40 km. We show that the equilibrium temperature and time are sensitive to the modifications in the collision frequencies and ionization rate based on the updated electron interaction cross sections.
NASA Astrophysics Data System (ADS)
Ajili, Y.; Abdallah, D. Ben; Al-Mogren, M. Mogren; Francisco, J. S.; Hochlaf, M.
2016-05-01
Three-dimensional potential energy surface (3D-PES) of the HNS-He interacting system in Jacobi coordinates is mapped using high-level ab initio theory. These computations are performed at the explicitly correlated coupled cluster method with single, double and perturbative triple excitations (CCSD(T)-F12) in conjunction with the augmented correlation-consistent aug-cc-pVTZ basis set. The 3D-PES is incorporated into quantum dynamical computations to treat the nuclear motions, where HNS is considered as a rigid rotator colliding with He. Cross-sections for transitions among the first twenty nine rotational levels of HNS (up to jKaKc = 92,8) are calculated using the quantum exact close-coupling method for total energies <1000 cm-1 and using the coupled state approximation for higher energies. Collisional rate constants for temperatures ranging from 5 to 200 K are deduced. A clear propensity rule in favour of Δj = -2 rotational transitions is observed. These rate coefficients are of great importance for the detection of HNS in interstellar medium.
NASA Astrophysics Data System (ADS)
Anders, R.; Chrysikopoulos, C. V.
2004-12-01
Batch experiments were conducted under both static and dynamic conditions to study the effects of temperature and the presence of sand on the inactivation process of viruses. The male--specific RNA coliphage, MS2, and the Salmonella typhimurium phage, PRD1, were used as model viruses for this study. Over 100 oven--baked borosilicate glass bottles with or without Monterey sand were filled with a low--ionic--strength phosphate buffered saline solution containing both bacteriophage and incubated at temperatures of 4o, 15o, or 25oC. The results of the batch experiments indicate that the inactivation process can be represented by a pseudo first-order expression with time--dependent rate coefficients. A combination of high temperature and the presence of sand appears to produce the greatest disruption to the surrounding protein coat of MS2. However, for PRD1, the lower activation energies derived from Arrhenius plots indicate a weaker dependence of the inactivation rate on temperature. Furthermore, the presence of an air--liquid--solid interface in the dynamic batch experiment containing sand produces the greatest damage to specific viral components of PRD1 that are required for infection. These results indicate the use of thermodynamic parameters based on the pseudo first--order inactivation expression allows better prediction of the inactivation of viruses in the environment.
G. WOOD
2000-12-01
Published breakthrough time, adsorption rate, and capacity data for components of organic vapor mixtures adsorbed from flows through fixed activated carbon beds have been analyzed. Capacities (as stoichiometric centers of constant pattern breakthrough curves) yielded stoichiometric times {tau}, which are useful for determining elution orders of mixture components. We also calculated adsorption rate coefficients k{sub v} of the Wheeler (or, more general Reaction Kinetic) breakthrough curve equation, when not reported, from breakthrough times and {tau}. Ninety-five k{sub v} (in mixture)/ k{sub v} (single vapor) ratios at similar vapor concentrations were calculated and averaged for elution order categories. For 43 first-eluting vapors the average ratio (1.07) was statistically no different (0.21 standard deviation) than unity, so that we recommend using the single-vapor k{sub v} for such. Forty-seven second-eluting vapor ratios averaged 0.85 (0.24 standard deviation), also not significantly different from unity; however, other evidence and considerations lead us recommend using k{sub v} (in mixture) = 0.85 k{sub v} (single vapor). Five third- and fourth-eluting vapors gave an average of 0.56 (0.16 standard deviation) for a recommended k{sub v} (in mixture) = 0.56 k{sub v} (single vapor) for such.
Papadimitriou, Vassileios C; Burkholder, James B
2016-08-25
Rate coefficients, k(T), for the OH radical + (E)-(CF3)2CFCH═CHF ((E)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, HFO-1438ezy(E)) gas-phase reaction were measured using pulsed laser photolysis-laser-induced fluorescence (PLP-LIF) between 214 and 380 K and 50 and 450 Torr (He or N2 bath gas) and with a relative rate method at 296 K between 100 and 400 Torr (synthetic air). Over the range of pressures included in this study, no pressure dependence in k(T) was observed. k(296 K) obtained using the two techniques agreed to within ∼3% with (3.26 ± 0.26) × 10(-13) cm(3) molecule(-1) s(-1) (2σ absolute uncertainty) obtained using the PLP-LIF technique. k(T) displayed non-Arrhenius behavior that is reproduced by (7.34 ± 0.30) × 10(-19)T(2) exp[(481 ± 10)/T) cm(3) molecule(-1) s(-1). With respect to OH reactive loss, the atmospheric lifetime of HFO-1438ezy(E) is estimated to be ∼36 days and HFO-1438ezy(E) is considered a very short-lived substance (VSLS) (the actual lifetime will depend on the time and location of the HFO-1438ezy(E) emission). On the basis of the HFO-1438ezy(E) infrared absorption spectrum measured in this work and its estimated lifetime, a radiative efficiency of 0.306 W m(-2) ppb(-1) (well-mixed gas) was calculated and its 100-year time-horizon global warming potential, GWP100, was estimated to be 8.6. CF3CFO, HC(O)F, and CF2O were identified using infrared spectroscopy as stable end products in the oxidation of HFO-1438ezy(E) in the presence of O2. Two additional fluorinated products were observed and theoretical calculations of the infrared spectra of likely degradation products are presented. The photochemical ozone creation potential of HFO-1438ezy(E) was estimated to be ∼2.15. PMID:27482844
NASA Astrophysics Data System (ADS)
Peirone, Silvina A.; Barrera, Javier A.; Taccone, Raúl A.; Cometto, Pablo M.; Lane, Silvia I.
2014-03-01
The relative rate technique was used to determine the rate coefficients of the reactions of OH radicals with (Z)-2-hexen-1-ol (k1), and (E)-3-hexen-1-ol (k2), at (296 ± 2) K and (750 ± 10) Torr of N2 or pure air. The reactions were investigated using a 200 L Teflon reaction chamber and a gas chromatograph coupled with flame-ionization detection. The following rate coefficients were derived, in units of cm3 mol-1 s-1: k1 = (1.1 ± 0.4) × 10-10 and k2 = (0.8 ± 0.1) × 10-10. This is the first experimental determination of k1 and k2. A comparison between the experimental rate coefficients (kexp) and the calculated rate coefficients using the structure-activity relationship (SAR) method (kSAR), for the reaction of different unsaturated alcohols with OH radicals is presented. The atmospheric lifetimes of the studied alcohols were estimated considering the rate coefficients of their reactions with OH and NO3 radicals. The radiative efficiencies (REs) were obtained from the infrared spectra of the two hexenols and the global warming potentials (GWPs) were then estimated. Atmospheric implications of the alcohols emission are briefly discussed.
NASA Astrophysics Data System (ADS)
McGillen, Max R.; Bernard, François; Fleming, Eric L.; Burkholder, James B.
2015-07-01
HCFC-133a (CF3CH2Cl), an ozone-depleting substance, is primarily removed from the atmosphere by gas-phase reaction with OH radicals and by UV photolysis. The rate coefficient, k, for the OH + HCFC-133a reaction was measured between 233 and 379 K and is given by k(T) = (9.32 ± 0.8) × 10-13 exp(-(1296 ± 28)/T), where k(296 K) was measured to be (1.10 ± 0.02) × 10-14 (cm3 molecule-1 s-1) (2σ precision uncertainty). The HCFC-133a UV absorption spectrum was measured between 184.95 and 240 nm at 213-323 K, and a spectrum parameterization is presented. The HCFC-133a atmospheric loss processes, lifetime, ozone depletion potential, and uncertainties were evaluated using a 2-D atmospheric model. The global annually averaged steady state lifetime and ozone depletion potential (ODP) were determined to be 4.45 (4.04-4.90) years and 0.017 (±0.001), respectively, where the ranges are based solely on the 2σ uncertainty in the kinetic and photochemical parameters. The infrared absorption spectrum of HCFC-133a was measured, and its global warming potential was determined to be 380 on the 100 year time horizon.
Miller, J.A.; Parrish, C.; Brown, N.J.
1986-07-17
Using the BAC-MP4 potential surface parameters of Melius and Binkley, we have predicted the thermal rate coefficients for the two reactions: O + HCN ..-->.. NCO + H (a) and O + HCN ..-->.. NH + CO (b). Several levels of approximation are used in the theoretical treatment: a, canonical theory; b, canonical theory with Wigner tunneling correction; c, microcanonical theory (energy conserving); d, microcanonical/J-conservative theory (conserves both energy and angular momentum); e, microcanonical/J-conservative theory with one-dimensional tunneling. At high temperature the available experimental results are predicted accurately by even the crudest theoretical treatment (canonical theory). At lower temperature the theoretical predictions using the basic BAC-MP4 parameters are too low. However, adjustments to the BAC-MP4 energy barriers within their stated error limits lead to satisfactory agreement with experiment over the entire temperature range where experimental results are available (500 to 2500 K). The most important results of the investigation concern the dependence of the predictions on the level of approximation. Each successive refinement in the theory produces larger values of k/sub b/. The details of the theoretical treatment and comparisons with experiment are described in detail.
Athiraman, Hemanthkumar; Jiang, Quan; Ding, Guang Liang; Zhang, Li; Zhang, Zheng Gang; Wang, Lei; Arbab, Ali S.; Li, Qingjiang; Panda, Swayam; Ledbetter, Karen; Rad, Ali M.; Chopp, Michael
2009-01-01
MRI has been used to evaluate labeled cell migration and distribution. However, quantitative determination of labeled cell concentration using MRI has not been systematically investigated. In the current study, we investigated the relationships between labeled cell concentration and MRI parameters of transverse relaxation rate, R2, and apparent diffusion coefficient (ADC), in vitro in phantoms and in vivo in rats after stroke. Significant correlations were detected between iron concentration or labeled cell concentration and MRI measurements of R2, ADC, and ADC×R2 in vitro. In contrast, in vivo labeled cell concentration did not significantly correlate with R2, ADC, and ADC×R2. A major factor for the absence of a significant correlation between labeled cell concentration and MRI measurements in vivo may be attributed to background effects of ischemic tissue. By correcting the background effects caused by ischemic damage, ΔR2 (difference in R2 values in the ischemic tissue with and without labeled cells) exhibited a significant correlation to labeled cell concentration. Our study suggests that MRI parameters have the potential to quantitatively determine labeled cell concentration in vivo. PMID:19107898
NASA Technical Reports Server (NTRS)
Feofilov, A. G.; Kutepov, A. A.; She, C. Y.; Smith, A. K.; Pesnell, W. D.; Goldberg, R. A.
2009-01-01
Among the processes governing the energy balance in the mesosphere and lower thermosphere (MLT), the quenching of CO2(V2) vibrational levels in collisions with oxygen atoms plays an important role. However, neither the rate coefficient of this process (k(CO2O)) nor the atomic oxygen concentrations ([O]) in the MLT are well known. The discrepancy between k(CO2O) measured in the lab and retrieved from atmospheric measurements is of about factor of 2.5. At the same time, the discrepancy between [O] in the MLT measured by different instruments is of the same order of magnitude. In this work we used a synergy of a ground based lidar and satellite infrared radiometer to make a further step in understanding of the physics of the region. In this study we apply the night- and daytime temperatures between 80 and 110 km measured by the Colorado State University narrow-band sodium (Na) lidar located at Fort Collins, Colorado for retrieving the product of k(CO2-O) x [O] from the limb radiances in the 15 micron channel measured by the SABER/TIMED instrument for nearly simultaneous common volume measurements of both instruments within +/-1 degree in latitude, +/-2 degrees in longitude and +/-10 minutes in time. We derive k(CO2-O) and its possible variation range from the retrieved product by utilizing the [O] values measured by the SABER and other instruments.
Teaching Absolute Value Meaningfully
ERIC Educational Resources Information Center
Wade, Angela
2012-01-01
What is the meaning of absolute value? And why do teachers teach students how to solve absolute value equations? Absolute value is a concept introduced in first-year algebra and then reinforced in later courses. Various authors have suggested instructional methods for teaching absolute value to high school students (Wei 2005; Stallings-Roberts…
NASA Astrophysics Data System (ADS)
Pamboundom, Mama; Tchakoua, Théophile; Nsangou, Mama
2016-04-01
In this work, inelastic rotational collision of AlCl with helium was studied. The CCSD(T) method was used for the computation of an accurate two dimensional potential energy surface (PES). In the calculation of the PES, Al-Cl bond was frozen at the experimental value 4.02678 a0. The aug-cc-pVQZ basis sets of Dunning was used throughout the computational process. This basis was completed with a set of 3s3p2d2f1g bond functions placed at mid-distance between the center of mass of AlCl and He atom for a better description of the van der Waals interaction energy. The PES of AlCl-He was found to have a global minimum at (R=8.65 a0, θ=0 degree), a local minimum at (R=7.45 a0, θ=82 degree) and a saddle point at (R=7.9 a0, θ=56 degree). The depths of the minima were 20.2 cm^{-1} and 19.8 cm^{-1} respectively for θ=0 and 84 degrees. The height of the saddle point with respect to the global minimum was 1.3 cm^{-1}. The PES, the result of an analytical fit, was expanded in terms of Legendre polynomials, then used for the evaluation of state-to-state rotational integral cross sections for the collision of AlCl with He in the close coupling approach. The collisional cross sections for the transitions occurring among the 17 first rotational levels of AlCl were calculated for kinetic energies up to 4000 cm^{-1}. Collisional rate coefficients between these rotational levels were computed for low and moderate kinetic temperatures ranging from 30 to 500 K. A propensity rule that favors odd Δ j transitions was found.
Radulović, Vladimir; Štancar, Žiga; Snoj, Luka; Trkov, Andrej
2014-02-01
The calculation of axial neutron flux distributions with the MCNP code at the JSI TRIGA Mark II reactor has been validated with experimental measurements of the (197)Au(n,γ)(198)Au reaction rate. The calculated absolute reaction rate values, scaled according to the reactor power and corrected for the flux redistribution effect, are in good agreement with the experimental results. The effect of different cross-section libraries on the calculations has been investigated and shown to be minor. PMID:24316530
Parker, James K; Payne, Walter A; Cody, Regina J; Nesbitt, Fred L; Stief, Louis J; Klippenstein, Stephen J; Harding, Lawrence B
2007-02-15
The rate coefficient has been measured under pseudo-first-order conditions for the Cl+CH3 association reaction at T=202, 250, and 298 K and P=0.3-2.0 Torr helium using the technique of discharge-flow mass spectrometry with low-energy (12-eV) electron-impact ionization and collision-free sampling. Cl and CH3 were generated rapidly and simultaneously by reaction of F with HCl and CH4, respectively. Fluorine atoms were produced by microwave discharge in an approximately 1% mixture of F2 in He. The decay of CH3 was monitored under pseudo-first-order conditions with the Cl-atom concentration in large excess over the CH3 concentration ([Cl]0/[CH3]0=9-67). Small corrections were made for both axial and radial diffusion and minor secondary chemistry. The rate coefficient was found to be in the falloff regime over the range of pressures studied. For example, at T=202 K, the rate coefficient increases from 8.4x10(-12) at P=0.30 Torr He to 1.8x10(-11) at P=2.00 Torr He, both in units of cm3 molecule-1 s-1. A combination of ab initio quantum chemistry, variational transition-state theory, and master-equation simulations was employed in developing a theoretical model for the temperature and pressure dependence of the rate coefficient. Reasonable empirical representations of energy transfer and of the effect of spin-orbit interactions yield a temperature- and pressure-dependent rate coefficient that is in excellent agreement with the present experimental results. The high-pressure limiting rate coefficient from the RRKM calculations is k2=6.0x10(-11) cm3 molecule-1 s-1, independent of temperature in the range from 200 to 300 K. PMID:17253663
NASA Technical Reports Server (NTRS)
Torr, D. G.; Orsini, N.
1978-01-01
The Atmosphere Explorer (AE) data are reexamined in the light of new laboratory measurements of the N2(+) recombination rate coefficient alpha. The new measurements support earlier measurements which yielded values of alpha significantly lower than the AE values. It is found that the values for alpha determined from the satellite data can be reconciled with the laboratory measurements, if the charge exchange rate coefficient for O(+)(2D) with N2 is less than one-quarter of that derived in the laboratory by Rutherford and Vroom (1971).
Papadimitriou, Vassileios C; Lazarou, Yannis G; Talukdar, Ranajit K; Burkholder, James B
2011-01-20
Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF
NASA Astrophysics Data System (ADS)
Tiemann, L. K.; Billings, S. A.
2010-12-01
Investigators appreciate the important role that nitrate (NO3-) and soil moisture availability can play in governing net N2O production from soils. However, a large knowledge gap remains surrounding the drivers of soil N2O consumption and the role of microbial adaptation to changing environmental conditions in governing both N2O production and consumption. Net N2O soil efflux can be correlated with temperature, but little is known about the influence of temperature on gross rates of N2O production vs. consumption. Further, we do not understand how microbial communities responsible for these processes adapt or acclimate to soil warming. To investigate whether temperature alters the denitrifier-mediated fate of NO3- lost via N2O or N2, and if any such effect changes across seasons, we incubated soil collected in three seasons at four temperatures with and without 15N-enriched nitrate for 26 hours. Incubations were conducted in an anaerobic environment flushed with helium to permit detection of N2O and N2, and those gases’ δ15N. Temperature positively influenced CO2 production resulting from anaerobic processes. Maximum values of net N2O production were positively influenced by incubation and seasonal temperature, and the maximum rate of net N2O production occurred relatively early at warmer incubation temperatures. We also observed greater N2O:N2 ratios early in the incubations at warmer incubation temperatures. Isotope data are consistent with these trends. For those soils receiving the 15N label, differences in δ15N2O between early and late in the incubations were increasingly negative, and differences in δ15N2 increasingly positive, as temperature increased. Q10 values for N2O production and consumption exhibited increasing similarities as seasons progressed, with June N2O production and consumption Q10 values being nearly identical. These data provide convincing evidence that: a) increasing temperatures can induce denitrifying communities to perform complete
Eosinophils; Absolute eosinophil count ... the white blood cell count to give the absolute eosinophil count. ... than 500 cells per microliter (cells/mcL). Normal value ranges may vary slightly among different laboratories. Talk ...
Liu, Zhijian; Liu, Kejun; Li, Hao; Zhang, Xinyu; Jin, Guangya; Cheng, Kewei
2015-01-01
Measurements of heat collection rate and heat loss coefficient are crucial for the evaluation of in service water-in-glass evacuated tube solar water heaters. However, conventional measurement requires expensive detection devices and undergoes a series of complicated procedures. To simplify the measurement and reduce the cost, software based on artificial neural networks for measuring heat collection rate and heat loss coefficient of water-in-glass evacuated tube solar water heaters was developed. Using multilayer feed-forward neural networks with back-propagation algorithm, we developed and tested our program on the basis of 915 measured samples of water-in-glass evacuated tube solar water heaters. This artificial neural networks-based software program automatically obtained accurate heat collection rate and heat loss coefficient using simply "portable test instruments" acquired parameters, including tube length, number of tubes, tube center distance, heat water mass in tank, collector area, angle between tubes and ground and final temperature. Our results show that this software (on both personal computer and Android platforms) is efficient and convenient to predict the heat collection rate and heat loss coefficient due to it slow root mean square errors in prediction. The software now can be downloaded from http://t.cn/RLPKF08. PMID:26624613
NASA Astrophysics Data System (ADS)
Quack, M.; Humbert, P.; van den Bergh, H.
1980-07-01
The influence of the three parameters (with two degrees of freedom) fluence, intensity, and time on rate coefficients and product yields in collisionless Unimolecular Reactions Induced by Monochromatic Infrared Radiation (URIMIR) is discussed in some detail in terms of the recently proposed logarithmic reactant fluence plots. Model calculations for several archetypes of such plots are presented, based on solutions of the Pauli master equation and solutions of the quantum mechanical equations of motion for spectra involving many states at each level of excitation. Linear diagrams, turnups, and turnovers are found and are discussed systematically. Experimental examples re-evaluated from the literature and new measurements on the laser induced decomposition of CF2HCl are reported which nicely illustrate the various theoretical possibilities. Steady state rate coefficients for six molecules are evaluated and summarized. In some situations the intrinsic nonlinear intensity dependence of the steady state rate coefficients and deviations from simple fluence dependence of the product yields both before and at steady state are shown to be important theoretically and experimentally. The role of the reducibility of the rate coefficient matrix is discussed in connection with turnovers and with the strong influence of initial temperature that is found in the laser induced decomposition of CF2HCl.
ERIC Educational Resources Information Center
Liu, Yan; Wu, Amery D.; Zumbo, Bruno D.
2010-01-01
In a recent Monte Carlo simulation study, Liu and Zumbo showed that outliers can severely inflate the estimates of Cronbach's coefficient alpha for continuous item response data--visual analogue response format. Little, however, is known about the effect of outliers for ordinal item response data--also commonly referred to as Likert, Likert-type,…
NASA Astrophysics Data System (ADS)
Zhu, Xi-Ming; Cheng, Zhi-Wen; Carbone, Emile; Pu, Yi-Kang; Czarnetzki, Uwe
2016-08-01
Electron-impact excitation processes play an important role in low-temperature plasma physics. Cross section and rate coefficient data for electron-impact processes from the ground state to excited states or between two excited states are required for both diagnostics and modeling works. However, the collisional processes between excited states are much less investigated than the ones involving the ground state due to various experimental challenges. Recently, a method for determining electron excitation rate coefficients between Ar excited states in afterglow plasmas was successfully implemented and further developed to obtain large sets of collisional data. This method combines diagnostics for electron temperature, electron density, and excited species densities and kinetic modeling of excited species, from which the electron excitation rate coefficients from one of the 1s states to the other 1s states or to one of 2p or 3p states are determined (states are in Paschen’s notation). This paper reviews the above method—namely the combined diagnostics and modeling in afterglow plasmas. The results from other important approaches, including electron-beam measurement of cross sections, laser pump-probe technique for measuring rate coefficients, and theoretical calculations by R-matrix and distorted-wave models are also discussed. From a comparative study of these results, a fitted mathematical expression of excitation rate coefficients is obtained for the electron temperature range of 1–5 eV, which can be used for the collisional-radiative modeling of low-temperature Ar plasmas. At last, we report the limitations in the present dataset and give some suggestions for future work in this area.
Werfelli, Ghofran; Halvick, Philippe; Honvault, Pascal; Kerkeni, Boutheïna; Stoecklin, Thierry
2015-09-21
The observed abundances of the methylidyne cation, CH(+), in diffuse molecular clouds can be two orders of magnitude higher than the prediction of the standard gas-phase models which, in turn, predict rather well the abundances of neutral CH. It is therefore necessary to investigate all the possible formation and destruction processes of CH(+) in the interstellar medium with the most abundant species H, H2, and e(-). In this work, we address the destruction process of CH(+) by hydrogen abstraction. We report a new calculation of the low temperature rate coefficients for the abstraction reaction, using accurate time-independent quantum scattering and a new high-level ab initio global potential energy surface including a realistic model of the long-range interaction between the reactants H and CH(+). The calculated thermal rate coefficient is in good agreement with the experimental data in the range 50 K-800 K. However, at lower temperatures, the experimental rate coefficient takes exceedingly small values which are not reproduced by the calculated rate coefficient. Instead, the latter rate coefficient is close to the one given by the Langevin capture model, as expected for a reaction involving an ion and a neutral species. Several recent theoretical works have reported a seemingly good agreement with the experiment below 50 K, but an analysis of these works show that they are based on potential energy surfaces with incorrect long-range behavior. The experimental results were explained by a loss of reactivity of the lowest rotational states of the reactant; however, the quantum scattering calculations show the opposite, namely, a reactivity enhancement with rotational excitation. PMID:26395702
NASA Astrophysics Data System (ADS)
Safronova, U. I.; Safronova, M. S.; Kato, T.
Excitation cross sections and rate coefficients by electron impact were calculated for the 1s22s - 1s2s2p, 1s22s - 1s2s2 and 1s22s - 1s2p2 transitions of the Li-like ions (C IV, N V, O VI, Ne VIII, Mg X, Al XI, Si XII, S XIV, Ar XVI, Ca XVIII, Ti XX, Fe XXIV, Ni XXVI, Zn XXVIII, Ge XXX, Se XXXII, Kr XXXIIV and Mo XXXX) by a Coulomb-Born approximation with exchange and including relativistic effects and configuration interactions. Level energies, mixing coefficients and transition wavelengths and probabilities were also computed.
Liu, Zhijian; Liu, Kejun; Li, Hao; Zhang, Xinyu; Jin, Guangya; Cheng, Kewei
2015-01-01
Measurements of heat collection rate and heat loss coefficient are crucial for the evaluation of in service water-in-glass evacuated tube solar water heaters. However, conventional measurement requires expensive detection devices and undergoes a series of complicated procedures. To simplify the measurement and reduce the cost, software based on artificial neural networks for measuring heat collection rate and heat loss coefficient of water-in-glass evacuated tube solar water heaters was developed. Using multilayer feed-forward neural networks with back-propagation algorithm, we developed and tested our program on the basis of 915measuredsamples of water-in-glass evacuated tube solar water heaters. This artificial neural networks-based software program automatically obtained accurate heat collection rateand heat loss coefficient using simply "portable test instruments" acquired parameters, including tube length, number of tubes, tube center distance, heat water mass in tank, collector area, angle between tubes and ground and final temperature. Our results show that this software (on both personal computer and Android platforms) is efficient and convenient to predict the heat collection rate and heat loss coefficient due to it slow root mean square errors in prediction. The software now can be downloaded from http://t.cn/RLPKF08. PMID:26624613
NASA Technical Reports Server (NTRS)
Dean, D. C.; Goldstein, J. I.
1984-01-01
The interdiffusion coefficient of FeNi in fcc taenite (gamma) of Fe-Ni and Fe-Ni-0.2 P alloys was measured as a function of temperature between 600 and 900 C. This temperature range is directly applicable to the nucleation and growth of the Widmanstatten pattern in iron meteorites and metal regions of stony and stony-iron meteorites. Diffusion couples were made from FeNi or FeNiP alloys which ensured that the couples were in the taenite phase at the diffusion temperature. The presence or absence of grain boundary diffusion was determined by measuring the Ni profile normal to the existing grain boundaries with the AEM. Ignoring any variation of interdiffusion coefficient with composition, the measured data was plotted versus the reciprocal of the diffusion temperature. The FeNi data generally follow the extrapolated Goldstein, et al. (1965) data from high temperatures. The FeNiP data indicates that small additions of P (0.2 wt%) cause a 3 to 10 fold increase in the FeNi interdifussion coefficient increasing with decreasing temperature. This increase is about the same as that predicted by Narayan and Goldstein (1983) at the Widmanstatten growth temperature.
Li, Yaqin; Sun, Zhigang E-mail: dawesr@mst.edu; Jiang, Bin; Guo, Hua E-mail: dawesr@mst.edu; Xie, Daiqian; Dawes, Richard E-mail: dawesr@mst.edu
2014-08-28
The kinetics and dynamics of several O + O{sub 2} isotope exchange reactions have been investigated on a recently determined accurate global O{sub 3} potential energy surface using a time-dependent wave packet method. The agreement between calculated and measured rate coefficients is significantly improved over previous work. More importantly, the experimentally observed negative temperature dependence of the rate coefficients is for the first time rigorously reproduced theoretically. This negative temperature dependence can be attributed to the absence in the new potential energy surface of a submerged “reef” structure, which was present in all previous potential energy surfaces. In addition, contributions of rotational excited states of the diatomic reactant further accentuate the negative temperature dependence.
Coefficients for Interrater Agreement.
ERIC Educational Resources Information Center
Zegers, Frits E.
1991-01-01
The degree of agreement between two raters rating several objects for a single characteristic can be expressed through an association coefficient, such as the Pearson product-moment correlation. How to select an appropriate association coefficient, and the desirable properties and uses of a class of such coefficients--the Euclidean…
Absolute nuclear material assay
Prasad, Manoj K.; Snyderman, Neal J.; Rowland, Mark S.
2012-05-15
A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.
Absolute nuclear material assay
Prasad, Manoj K.; Snyderman, Neal J.; Rowland, Mark S.
2010-07-13
A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.
Niane, Aliou; Dath, Cheikh Amadou Bamba; Faye, Ndèye Arame Boye; Hammami, Kamel; Jaidane, Nejm-Eddine
2014-01-01
A theoretical study of rotational collision of LiH(X(1)Σ(+),v = 0, J) with Ar has been carried out. The ab initio potential energy surface (PES) describing the interaction between the Ar atom and the rotating LiH molecule has been calculated very accurately and already discussed in our previous work [Computational and Theoretical Chemistry 993 (2012) 20-25]. This PES is employed to evaluate the de-excitation cross sections. The ab initio PES for the LiH(X(1)Σ(+))-Ar((1)S) Van der waals system is calculated at the coupled-cluster [CCSD(T)] approximation for a LiH length fixed to an experimental value of 3.0139 bohrs. The basis set superposition error (BSSE) is corrected and the bond functions are placed at mid-distance between the center of mass of LiH and the Ar atom. The cross sections are then derived in the close coupling (CC) approach and rate coefficients are inferred by averaging these cross sections over a Maxwell-Boltzmann distribution of kinetic energies. The 11 first rotational levels of rate coefficients are evaluated for temperatures ranging from 10 to 300 K. We notice that the de-excitation rate coefficients appear large in the order 10(-10) cm(-3) s(-1) and show very low temperature dependence. The rate coefficients magnify significantly the propensity toward ∆ J = -1 transitions. These results confirm the same propensity already noted for the cross sections. PMID:24808997
NASA Astrophysics Data System (ADS)
Hernández Vera, M.; Lique, F.; Kłos, J.; Dumouchel, F.; Rubayo Soneira, J.
2015-08-01
Accurate determination of collisional rate coefficients is an essential step in the estimation of the SiCN and SiNC abundances in the interstellar and circumstellar media. In this paper, we carry out calculations of rate coefficients for the rotational (de-)excitation of SiCN and SiNC molecules in collision with He. The calculations are based on new two-dimensional potential energy surfaces obtained from highly correlated ab initio calculations. Coupled-States quantum approximation was used in the scattering calculations to obtain collisional (de-)excitation cross-sections of SiCN and SiNC by He. The spin-orbit coupling and Λ-doublet splitting of SiCN and SiNC levels were taken into account explicitly. Rate coefficients for transitions among the first 92 rotational levels of SiCN and SiNC were calculated for temperatures ranging from 5 to 100 K. Moderate differences exist between the rate coefficients of both isomers. Subsequently, the new collisional data are used to simulate the excitation of SiCN and SiNC in the circumstellar gas. We obtain the brightness and excitation temperatures of selected lines frequently observed towards the circumstellar envelopes and we find that local thermodynamic equilibrium conditions are not fulfilled for these species. Radiative transfer calculations are then needed in order to accurately determine their abundances. Our results also show that previous estimations of the cyanides/isocyanides abundance ratios were incorrect and the present calculations show that SiCN, the most stable isomer, is more abundant than SiNC. This shows again the evidence of selective cyanide chemistry.
NASA Technical Reports Server (NTRS)
Savin, D. W.; Badnell, N. R.; Bartsch, T.; Brandau, C.; Chen, M. H.; Grieser, M.; Gwinner, G.; Hoffknecht, A.; Kahn, S. M.; Linkemann, J.
2000-01-01
Iron L-shell ions (Fe XVII to Fe XXIV) play an important role in determining the line emission and thermal and ionization structures of photoionized gases. Existing uncertainties in the theoretical low temperature dielectronic recombination (DR) rate coefficients for these ions significantly affects our ability to model and interpret observations of photoionized plasmas. To help address this issue, we have initiated a laboratory program to produce reliable low temperature DR rates. Here, we present some of our recent results and discuss some of their astrophysical implications.
NASA Technical Reports Server (NTRS)
Banks, M.; Bridges, N. T.; Benzit, M.
2005-01-01
Knowledge of the rates at which rocks abrade from the impact of saltating sand provides important input into estimating the age and degree of modification of arid surfaces on Earth and Mars. Previous work has relied on measuring mass loss rates in the field and the laboratory. The susceptibility of rocks and other natural materials has been quantified on a relative scale from laboratory studies.
Santos, M V; Sansinena, M; Zaritzky, N; Chirife, J
2012-01-01
In oocyte vitrification, plunging directly into liquid nitrogen favor film boiling and strong nitrogen vaporization. A survey of literature values of heat transfer coefficients (h) for film boiling of small metal objects with different geometries plunged in liquid nitrogen revealed values between 125 to 1000 W per per square m per K. These h values were used in a numerical simulation of cooling rates of two oocyte vitrification devices (open-pulled straw and Cryotop), plunged in liquid and slush nitrogen conditions. Heat conduction equation with convective boundary condition was considered a linear mathematical problem and was solved using the finite element method applying the variational formulation. COMSOL Multiphysics was used to simulate the cooling process of the systems. Predicted cooling rates for OPS and Cryotop when cooled at -196 degree C (liquid nitrogen) or -207 degree C (average for slush nitrogen) for heat transfer coefficients estimated to be representative of film boiling, indicated lowering the cooling temperature produces only a maximum 10 percent increase in cooling rates; confirming the main benefit of plunging in slush over liquid nitrogen does not arise from their temperature difference. Numerical simulations also demonstrated that a hypothetical four-fold increase in the cooling rate of vitrification devices when plunging in slush nitrogen would be explained by an increase in heat transfer coefficient. This improvement in heat transfer (i.e., high cooling rates) in slush nitrogen is attributed to less or null film boiling when a sample is placed in slush (mixture of liquid and solid nitrogen) because it first melts the solid nitrogen before causing the liquid to boil and form a film. PMID:22434120
Kirikae, M.; Diksic, M.; Yamamoto, Y.L.
1988-08-01
An autoradiographic method for the measurement of the rate of valine incorporation into brain proteins is described. The transfer coefficients for valine into and out of the brain and the rate of valine incorporation into normal rat brain proteins are given. The valine incorporation and the transfer constants of valine between different biological compartments are provided for 14 gray matter and 2 white matter structures of an adult rat brain. The rate of valine incorporation varies between 0.52 +/- 0.19 nmol/g/min in white matter and 1.94 +/- 0.47 in inferior colliculus (gray matter). Generally, the rate of valine incorporation is about three to four times higher in the gray matter than in the white matter structures.
NASA Astrophysics Data System (ADS)
Meng, Qingyong; Chen, Jun; Zhang, Dong H.
2015-09-01
The ring polymer molecular dynamics (RPMD) calculations are performed to calculate rate constants for the title reaction on the recently constructed potential energy surface based on permutation invariant polynomial (PIP) neural-network (NN) fitting [J. Li et al., J. Chem. Phys. 142, 204302 (2015)]. By inspecting convergence, 16 beads are used in computing free-energy barriers at 300 K ≤ T ≤ 1000 K, while different numbers of beads are used for transmission coefficients. The present RPMD rates are in excellent agreement with quantum rates computed on the same potential energy surface, as well as with the experimental measurements, demonstrating further that the RPMD is capable of producing accurate rates for polyatomic chemical reactions even at rather low temperatures.
Mass transfer between aquifer material and groundwater is often modeled as first-order rate-limited sorption or diffusive exchange between mobile zones and immobile zones with idealized geometries. Recent improvements in experimental techniques and advances in our understanding o...
Rate Coefficient for the (4)Heμ + CH4 Reaction at 500 K: Comparison between Theory and Experiment.
Arseneau, Donald J; Fleming, Donald G; Li, Yongle; Li, Jun; Suleimanov, Yury V; Guo, Hua
2016-03-01
The rate constant for the H atom abstraction reaction from methane by the muonic helium atom, Heμ + CH4 → HeμH + CH3, is reported at 500 K and compared with theory, providing an important test of both the potential energy surface (PES) and reaction rate theory for the prototypical polyatomic CH5 reaction system. The theory used to characterize this reaction includes both variational transition-state (CVT/μOMT) theory (VTST) and ring polymer molecular dynamics (RPMD) calculations on a recently developed PES, which are compared as well with earlier calculations on different PESs for the H, D, and Mu + CH4 reactions, the latter, in particular, providing for a variation in atomic mass by a factor of 36. Though rigorous quantum calculations have been carried out for the H + CH4 reaction, these have not yet been extended to the isotopologues of this reaction (in contrast to H3), so it is important to provide tests of less rigorous theories in comparison with kinetic isotope effects measured by experiment. In this regard, the agreement between the VTST and RPMD calculations and experiment for the rate constant of the Heμ + CH4 reaction at 500 K is excellent, within 10% in both cases, which overlaps with experimental error. PMID:26484648
NASA Astrophysics Data System (ADS)
Jubb, A. M.; Gierczak, T.; Baasandorj, M.; Waterland, R. L.; Burkholder, J. B.
2013-12-01
Mixtures of methyl-perfluoroheptene-ethers (C7F13OCH3, MPHEs) are currently in use as a replacement for perfluorinated alkane (PFC) and polyether mixtures (both persistent greenhouse gases with atmospheric lifetimes >1000 years) used as heat transfer fluids. Currently, the atmospheric fate of the MPHE isomers are not well characterized, however, reaction with the OH radical is expected to be a dominant tropospheric loss process for these compounds. In order to assess the atmospheric lifetimes and environmental implications of MPHE use, rate coefficients for MPHE isomers' reaction with OH radicals are desired. In the work presented here, rate coefficients, k, for the gas-phase reaction of the OH radical with six MPHEs commonly used in commercial mixtures (isomers and stereoisomers) and their deuterated analogs (d3-MPHE) were determined at 296 K using a relative rate method with combined gas-chromatography/IR spectroscopy detection. A range of OH rate coefficient values was observed, up to a factor of 20× different, between the MPHE isomers with the (E)-stereoisomers exhibiting the greatest reactivity. The measured OH reaction rate coefficients for the d3-MPHE isomers were lower than the observed MPHE values although a large range of k values between isomers was still observed. The reduction in reactivity with deuteration signifies that the MPHE + OH reaction proceeds via both addition to the olefinic C=C bond and H-abstraction from the methyl ester group. OH addition to the C=C bond was determined to be the primary reaction channel. Atmospheric lifetimes with respect to the OH reaction for the six MPHE isomers were found to be in the range of days to months. The short lifetimes indicate that MPHE use will primarily impact tropospheric local and regional air quality. A MPHE atmospheric degradation mechanism will be presented. As part of this work, radiative efficiencies and global warming potentials (GWPs) for the MPHE isomers were estimated based on measured
NASA Astrophysics Data System (ADS)
Górecki, Kamil; Bala, Piotr; Cios, Grzegorz; Koziel, Tomasz; Stępień, Milena; Wieczerzak, Krzysztof
2016-07-01
An influence of two different cooling rates on the microstructure and dispersion of the components of high-entropy alloy from Al-Ti-Co-Ni-Fe system has been examined. For investigated alloys, the effective partitioning coefficient has been calculated. This factor indicates the degree of segregation of elements and allows for the specification of the differences between dendrites and interdendritic regions. The obtained results allow for the conclusion that the cooling rate substantially affect the growth of dendrites and the volume fraction of interdendritic regions as well as the partitioning of elements in the alloy. Furthermore, the obtained results made it possible to compare the influence of the cooling rate and the chemical composition on the dispersion of the alloying elements.
NASA Astrophysics Data System (ADS)
Górecki, Kamil; Bala, Piotr; Cios, Grzegorz; Koziel, Tomasz; Stępień, Milena; Wieczerzak, Krzysztof
2016-04-01
An influence of two different cooling rates on the microstructure and dispersion of the components of high-entropy alloy from Al-Ti-Co-Ni-Fe system has been examined. For investigated alloys, the effective partitioning coefficient has been calculated. This factor indicates the degree of segregation of elements and allows for the specification of the differences between dendrites and interdendritic regions. The obtained results allow for the conclusion that the cooling rate substantially affect the growth of dendrites and the volume fraction of interdendritic regions as well as the partitioning of elements in the alloy. Furthermore, the obtained results made it possible to compare the influence of the cooling rate and the chemical composition on the dispersion of the alloying elements.
Scheibe, Timothy D.
2002-10-28
In granular porous media, bacterial transport is often modeled using the advection-dispersion transport equation, modified to account for interactions between the bacteria and grain surfaces (attachment and detachment) using a linear kinetic reaction model. In this paper we examine the relationships among the parameters of the above model in the context of bacterial transport for bioaugmentation. In this context, we wish to quantify the distance to which significant concentrations of bacteria can be transported, as well as the uniformity with which they can be distributed within the subsurface. Because kinetic detachment rates (Kr) are typically much smaller than corresponding attachment rates (Kf), the attachment rate exerts primary control on the distance of bacterial transport. Hydraulic conductivity (K) also plays a significant role because of its direct relationship to the advective velocity and its typically high degree of spatial variability at field scales. Because Kf is related to the velocity, grain size, and porosity of the medium, as is K, we expect that there exists correlation between these two parameters. Previous investigators have assumed a form of correlation between Kf and ln(K) based in part on reparameterization of clean-bed filtration equations in terms of published relations between grain size, effective porosity, and ln(K). The hypotheses examined here are that (1) field-scale relationships between K and Kf can be developed by combining a number of theoretical and empirical results in the context of a heterogeneous aquifer flow model (following a similar approach to previous investigators with some extensions), and (2) correlation between K and Kf will enhance the distance of field-scale bacterial transport in granular aquifers. We test these hypotheses using detailed numerical models and observations of field-scale bacterial transport in a shallow sandy aquifer within the South Oyster Site near Oyster, Virginia, USA.
Corman, Gregory Scot; Dean, Anthony John; Tognarelli, Leonardo; Pecchioli, Mario
2005-06-28
A structure for attaching together or sealing a space between a first component and a second component that have different rates or amounts of dimensional change upon being exposed to temperatures other than ambient temperature. The structure comprises a first attachment structure associated with the first component that slidably engages a second attachment structure associated with the second component, thereby allowing for an independent floating movement of the second component relative to the first component. The structure can comprise split rings, laminar rings, or multiple split rings.
NASA Technical Reports Server (NTRS)
Hoobler, Ray J.; Leone, Stephen R.
1997-01-01
Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.
Sadana, A
1998-01-01
The diffusion-limited binding kinetics of antigen (analyte), in solution with antibody (receptor) immobilized on a biosensor surface, is analyzed within a fractal framework. Most of the data presented is adequately described by a single-fractal analysis. This was indicated by the regression analysis provided by Sigmaplot. A single example of a dual-fractal analysis is also presented. It is of interest to note that the binding-rate coefficient (k) and the fractal dimension (Df) both exhibit changes in the same and in the reverse direction for the antigen-antibody systems analyzed. Binding-rate coefficient expressions, as a function of the Df developed for the antigen-antibody binding systems, indicate the high sensitivity of the k on the Df when both a single- and a dual-fractal analysis are used. For example, for a single-fractal analysis, and for the binding of antibody Mab 0.5 beta in solution to gp120 peptide immobilized on a BIAcore biosensor, the order of dependence on the Df was 4.0926. For a dual-fractal analysis, and for the binding of 25-100 ng/mL TRITC-LPS (lipopolysaccharide) in solution with polymyxin B immobilized on a fiberoptic biosensor, the order of dependence of the binding-rate coefficients, k1 and k2, on the fractal dimensions, Df1 and Df2, were 7.6335 and -11.55, respectively. The fractional order of dependence of the k(s) on the Df(s) further reinforces the fractal nature of the system. The k(s) expressions developed as a function of the Df(s) are of particular value, since they provide a means to better control biosensor performance, by linking it to the heterogeneity on the surface, and further emphasize, in a quantitative sense, the importance of the nature of the surface in biosensor performance. PMID:9779572
NASA Astrophysics Data System (ADS)
Schütze, Nicole; Zhong, Xiaoyin; Kirschbaum, Stefan; Bejan, Iustinian; Barnes, Ian; Benter, Thorsten
2010-12-01
Relative kinetic studies have been performed on the reactions of Cl atoms with a series of methyl alkyl esters in a 405-liter borosilicate glass chamber at (298 ± 3) K and one atmosphere of synthetic air using in situ FTIR spectroscopy to monitor the reactants. Rate coefficients (in units of cm 3 molecule -1 s -1) were determined for the following compounds: methyl acetate (2.48 ± 0.58) × 10 -12; methyl propanoate (1.68 ± 0.36) × 10 -11; methyl butanoate (4.77 ± 0.87) × 10 -11; methyl pentanoate (7.84 ± 1.15) × 10 -11; methyl hexanoate (1.09 ± 0.31) × 10 -10; methyl heptanoate (1.56 ± 0.37) × 10 -10; methyl cyclohexane carboxylate (3.32 ± 0.76) × 10 -10; methyl-2-methyl butanoate (9.41 ± 1.39) × 10 -11. In addition rate coefficients (in units of 10 -11 cm 3 molecule -1 s -1) have been obtained for the reactions of OH radicals with the following compounds: methyl butanoate (3.55 ± 0.71), methyl pentanoate (5.41 ± 1.08), and methyl-2-methyl butanoate (4.08 ± 0.82). Using the kinetic rate data tropospheric lifetimes for the methyl alkyl esters with respect to their reactions with OH, and Cl have been estimated for typical ambient air concentrations of these oxidants.
NASA Astrophysics Data System (ADS)
Urpi, Luca; Rinaldi, Antonio Pio; Rutqvist, Jonny; Cappa, Frédéric; Spiers, Christopher J.
2016-04-01
Poro-elastic stress and effective stress reduction associated with deep underground fluid injection can potentially trigger shear rupture along pre-existing faults. We modeled an idealized CO2 injection scenario, to assess the effects on faults of the first phase of a generic CO2 aquifer storage operation. We used coupled multiphase fluid flow and geomechanical numerical modeling to evaluate the stress and pressure perturbations induced by fluid injection and the response of a nearby normal fault. Slip-rate dependent friction and inertial effects have been aken into account during rupture. Contact elements have been used to take into account the frictional behavior of the rupture plane. We investigated different scenarios of injection rate to induce rupture on the fault, employing various fault rheologies. Published laboratory data on CO2-saturated intact and crushed rock samples, representative of a potential target aquifer, sealing formation and fault gouge, have been used to define a scenario where different fault rheologies apply at different depths. Nucleation of fault rupture takes place at the bottom of the reservoir, in agreement with analytical poro-elastic stress calculations, considering injection-induced reservoir inflation and the tectonic scenario. For the stress state here considered, the first triggered rupture always produces the largest rupture length and slip magnitude, correlated with the fault rheology. Velocity weakening produces larger ruptures and generates larger magnitude seismic events. Heterogeneous faults have been considered including velocity-weakening or velocity strengthening sections inside and below the aquifer, while upper sections being velocity-neutral. Nucleation of rupture in a velocity strengthening section results in a limited rupture extension, both in terms of maximum slip and rupture length. For a heterogeneous fault with nucleation in a velocity-weakening section, the rupture may propagate into the overlying velocity
McLeod, Stephen
2014-07-01
Absolute needs (as against instrumental needs) are independent of the ends, goals and purposes of personal agents. Against the view that the only needs are instrumental needs, David Wiggins and Garrett Thomson have defended absolute needs on the grounds that the verb 'need' has instrumental and absolute senses. While remaining neutral about it, this article does not adopt that approach. Instead, it suggests that there are absolute biological needs. The absolute nature of these needs is defended by appeal to: their objectivity (as against mind-dependence); the universality of the phenomenon of needing across the plant and animal kingdoms; the impossibility that biological needs depend wholly upon the exercise of the abilities characteristic of personal agency; the contention that the possession of biological needs is prior to the possession of the abilities characteristic of personal agency. Finally, three philosophical usages of 'normative' are distinguished. On two of these, to describe a phenomenon or claim as 'normative' is to describe it as value-dependent. A description of a phenomenon or claim as 'normative' in the third sense does not entail such value-dependency, though it leaves open the possibility that value depends upon the phenomenon or upon the truth of the claim. It is argued that while survival needs (or claims about them) may well be normative in this third sense, they are normative in neither of the first two. Thus, the idea of absolute need is not inherently normative in either of the first two senses. PMID:23586876
NASA Astrophysics Data System (ADS)
Nahar, Sultana N.
2008-03-01
The inverse process of photoionization and electron-ion recombination of (h +SXIV SXV+e) and (h +SXV SXVI +e) are studied in details using ab into unified method that provides self-consistent sets of results for these processes. Results are presented for large number of fine structure levels where n 10 and 0 l 9; 98 levels for Li-likes S XIV with 1/2 J 17/2 and 188 levels for He-like S XV with 0 J 10. Photoionization cross section, :PI, of the levels of both S XIV and SXV decay smoothly in the lower region. However, narrow and high peak autoionizing Rhydberg series resonances belonging to various excited core levels appear in the high energy region and enhance the background cross section of the excited levels. The resonance series of n=2 core levels dominate while they become weaker with higher n. The prominent feature is the enhacement of the background cross section at n=2 core thresholds due to K-shell ionization leaving the ion in excited 2p states. PI also show wide PEG (photo-excitation-of-core) resonances at the photon energies that equal to the core excitation energies, Level-specific photoionization cross sections, PI(nSLJ), and recombination rate coefficients, σRC(nSLJ),are obtained for the first time for these ions. Currently available results correspond to photoionization for 18 terms with missing features and to only total recombination rate coefficients. Present σRc(nSLJ) incorporates both the radiative recombination (RR) and dielectronic recombination (DR), and show a "bump" or "shoulder" in the high temperature region due to DR dominace. The total unified recombination rate coefficients show good agreement with the available RR, and DR rates. Recombination rates photoelectron energy are presented for the astrophysical and laboratory plasma applications. Total recombination rates for H-like S XVI are given for completeness. The The results should be accurate within 10-15% based on the unified method that includes important atomic effects such as
Altitude Variation of the CO2(V2)-O Quenching Rate Coefficient in Mesosphere and Lower Thermosphere
NASA Technical Reports Server (NTRS)
Feofilov, A.; Kutepov, A.; She, C.; Smith, A. K.; Pesnell, W. D.; Goldberg, R. A.
2010-01-01
Among the processes governing the energy balance in the mesosphere and lower thermosphere (MLT), the quenching of CO2(v2) vibrational levels by collisions with oxygen atoms plays an important role. However, the k(CO2-O) values measured in the lab and retrieved from atmospheric measurements vary from 1.5 x 10(exp -12)cu cm/s through 9.0 x 10(exp -12)cu cm/s that requires further studying. In this work we used synergistic data from a ground based lidar and a satellite infrared radiometer to estimate k(CO2-O). We used the night- and daytime temperatures between 80 and 110 km measured by the Colorado State University narrow-band sodium (Na) lidar located at Fort Collins, Colorado (41 N, 255E) as ground truth of the SABER/TIMED nearly simultaneous ( +/-10 minutes) and common volume (within +/-1 degree in latitude, +/-2 degrees in longitude) observations. For each altitude in 80-110 km interval we estimate an 'optimal" value of k(CO2-O) needed to minimize the discrepancy between the simulated 15 micron CO2 radiance and that measured by the SABER/TIMED instrument. The k(CO2-O) obtained in this way varies in altitude from 3.5 x 10(exp -12)cu cm/s at 80 km to 5.2 x 10(exp -12)cu cm/s for altitudes above 95 km. We discuss this variation of the rate constant and its impact on temperature retrievals from 15 pm radiance measurements and on the energy budget of MLT.
Altitude Variation of the CO2 (V2)-O Quenching Rate Coefficient in Mesosphere and Lower Thermosphere
NASA Technical Reports Server (NTRS)
Feofilovi, Artem; Kutepov, Alexander; She, Chiao-Yao; Smith, Anne K.; Pesnell, William Dean; Goldberg, Richard A.
2010-01-01
Among the processes governing the energy balance in the mesosphere and lower thermosphere (mlt), the quenching of CO2(N2) vibrational levels by collisions with oxygen atoms plays an important role. However, the k(CO2-O) values measured in the lab and retrieved from atmospheric measurements vary from 1.5 x 10(exp -12) cubic centimeters per second through 9.0 x 10(exp -12) cubic centimeters per second that requires further studying. In this work we used synergistic data from a ground based lidar and a satellite infrared radiometer to estimate K(CO2-O). We used the night- and daytime temperatures between 80 and 110 km measured by the colorado state university narrow-band sodium (Na) lidar located at fort collins, colorado (41N, 255E) as ground truth of the saber/timed nearly simultaneous (plus or minus 10 minutes) and common volume (within plus or minus 1 degree in latitude, plus or minus 2 degrees in longitude) observations. For each altitude in 80-110 km interval we estimate an "optimal" value of K(CO2-O) needed to minimize the discrepancy between the simulated 15 mm CO2 radiance and that measured by the saber/timed instrument. The K(CO2-O) obtained in this way varies in altitude from 3.5 x 10(exp -12) cubic centimeters per second at 80 km to 5.2 x 10(exp -12) cubic centimeters pers second for altitudes above 95 km. We discuss this variation of the rate constant and its impact on temperature retrievals from 15 mm radiance measurements and on the energy budget of mlt.
NASA Technical Reports Server (NTRS)
Michael, J. V.; Whytock, D. A.; Lee, J. H.; Payne, W. A.; Stief, L. J.
1977-01-01
Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.
NASA Astrophysics Data System (ADS)
Kirillov, A. S.
2014-01-01
The removal rates of Herzberg states of molecular oxygen O2(cΣu-, v = 0-16), O2(AΔu, v = 0-11), O2(AΣu+, v = 0-10) in the collisions with ground-state CO2, CO, N2, O2 molecules are calculated according to analytical expressions. The study includes a consideration of intramolecular electron energy transfers without and with vibrational excitation of target molecules and intermolecular processes. The preliminary calculations show important role of electronic-vibrational energy transfer processes in the quenching O2(AΣu+, v) + CO2; O2(cΣu-, v) + CO2, CO, N2; O2(AΔu, v) + O2. Reasonable agreement of the calculated rate coefficients with data of laser experimental measurements is obtained.
NASA Astrophysics Data System (ADS)
McLaughlin, B. M.; Gorczyca, T. W.; Keenan, F. P.; Bell, K. L.
2001-12-01
Photoionization cross-sections out of the fine-structure levels (2s22p4 3P2,0,1) of the O-like Fe ion FeXIX have been reinvestigated. Data for photoionization out of each of these fine-structure levels have been obtained, where the calculations have been performed with and without the inclusion of radiation damping on the resonance structure in order to assess the importance of this process. Recombination rate coefficients are determined using the Milne relation, for the case of an electron recombining with N-like Fe ions (FeXX) in the ground state to form O-like Fe (FeXIX) existing in each of the fine-structure ground-state levels. Recombination rates are presented over a temperature range ~4.0<=logTe<=7.0, of importance to the modelling of X-ray emission plasmas.
NASA Technical Reports Server (NTRS)
Georgevic, R. M.
1973-01-01
Closed-form analytic expressions for the time variations of instantaneous orbital parameters and of the topocentric range and range rate of a spacecraft moving in the gravitational field of an oblate large body are derived using a first-order variation of parameters technique. In addition, the closed-form analytic expressions for the partial derivatives of the topocentric range and range rate are obtained, with respect to the coefficient of the second harmonic of the potential of the central body (J sub 2). The results are applied to the motion of a point-mass spacecraft moving in the orbit around the equatorially elliptic, oblate sun, with J sub 2 approximately equal to .000027.
Kanno, Nozomu; Tani, Hiroumi; Daimon, Yu; Terashima, Hiroshi; Yoshikawa, Norihiko; Koshi, Mitsuo
2015-07-16
The reactions of NO2 with cis-/trans-CH3NHNH, CH3NNH2 and CH2NHNH2 have been studied theoretically by quantum chemical calculations and steady-state unimolecular master equation analysis based on RRKM theory. The barrier heights for the roaming transition states between nitro (RNO2) and nitrite (RONO) isomerization reactions and those for the concerted HONO and HNO2 elimination reactions from RNO2 and RONO, affect the pressure dependences of the product-specific rate coefficients. At ambient temperature and pressure, the dominant product of the reactions of NO2 with cis-/trans-CH3NHNH and CH2NHNH2 would be expected to be HONO with trans-CH3NNH and CH2NNH2, respectively, whereas it is CH3N(NH2)NO2 for CH3NNH2 + NO2. The product-specific rate coefficients for the titled and related reactions on the same potential energy surfaces were proposed for kinetics modeling. PMID:25970048
NASA Astrophysics Data System (ADS)
Meng, Qingyong; Chen, Jun; Zhang, Dong H.
2016-04-01
To fast and accurately compute rate coefficients of the H/D + CH4 → H2/HD + CH3 reactions, we propose a segmented strategy for fitting suitable potential energy surface (PES), on which ring-polymer molecular dynamics (RPMD) simulations are performed. On the basis of recently developed permutation invariant polynomial neural-network approach [J. Li et al., J. Chem. Phys. 142, 204302 (2015)], PESs in local configuration spaces are constructed. In this strategy, global PES is divided into three parts, including asymptotic, intermediate, and interaction parts, along the reaction coordinate. Since less fitting parameters are involved in the local PESs, the computational efficiency for operating the PES routine is largely enhanced by a factor of ˜20, comparing with that for global PES. On interaction part, the RPMD computational time for the transmission coefficient can be further efficiently reduced by cutting off the redundant part of the child trajectories. For H + CH4, good agreements among the present RPMD rates and those from previous simulations as well as experimental results are found. For D + CH4, on the other hand, qualitative agreement between present RPMD and experimental results is predicted.
NASA Astrophysics Data System (ADS)
Barta, J.; Costa, M.; Van Haren, J. L. M.; Pangle, L. A.; Troch, P. A. A.
2014-12-01
In order to understand the biological processes taking place on an experimental hillslope with vegetation, it is important to know the amount of gasses such as oxygen and carbon dioxide being produced and consumed. When studying the gas exchange rates in a closed system like the Landscape Evolution Observatory (LEO), one must take into account gas that is being lost or gained from other sources. Aside from biogeochemical processes, gas concentrations in the LEO atmosphere may change due to leakage to the outside environment and diffusion into the soil. To quantify these fluxes, two constants must be determined experimentally: the gas leakage constant L and the coefficient of diffusion for the hillslope soil. To accomplish this, a tracer gas, sulfur hexafluoride, was injected into the sealed east bay chamber and syringes were used to take samples periodically from the airspace and from the hillslope soil. The relative sulfur hexafluoride concentrations were then analyzed with a SRI 8610c gas chromatograph. By analyzing both the the airspace concentration decay as well as the concentration in the soil, the chamber's leakage constant was determined to be and the soil diffusion coefficient was also determined. Once these values are experimentally quantified, they can be used in equations to quantify the rate of gas leakage and soil diffusion of more important gases such as carbon dioxide and oxygen.
NASA Technical Reports Server (NTRS)
Feofilov, A. G.; Kutepov, A. A.; She, C.-Y.; Smith, A. K.; Pesnell, W. D.; Goldberg, R. A.
2012-01-01
Among the processes governing the energy balance in the mesosphere and lower thermosphere (MLT), the quenching of CO2(nu2) vibrational levels by collisions with O atoms plays an important role. However, there is a factor of 3-4 discrepancy between the laboratory measurements of the CO2-O quenching rate coefficient, k(sub VT),and its value estimated from the atmospheric observations. In this study, we retrieve k(sub VT) in the altitude region85-105 km from the coincident SABER/TIMED and Fort Collins sodium lidar observations by minimizing the difference between measured and simulated broadband limb 15 micron radiation. The averaged k(sub VT) value obtained in this work is 6.5 +/- 1.5 X 10(exp -12) cubic cm/s that is close to other estimates of this coefficient from the atmospheric observations.However, the retrieved k(sub VT) also shows altitude dependence and varies from 5.5 1 +/-1 10(exp -12) cubic cm/s at 90 km to 7.9 +/- 1.2 10(exp -12) cubic cm/s at 105 km. Obtained results demonstrate the deficiency in current non-LTE modeling of the atmospheric 15 micron radiation, based on the application of the CO2-O quenching and excitation rates, which are linked by the detailed balance relation. We discuss the possible model improvements, among them accounting for the interaction of the non-thermal oxygen atoms with CO2 molecules.
Absolute Value Boundedness, Operator Decomposition, and Stochastic Media and Equations
NASA Technical Reports Server (NTRS)
Adomian, G.; Miao, C. C.
1973-01-01
The research accomplished during this period is reported. Published abstracts and technical reports are listed. Articles presented include: boundedness of absolute values of generalized Fourier coefficients, propagation in stochastic media, and stationary conditions for stochastic differential equations.
NASA Astrophysics Data System (ADS)
Bisetti, Fabrizio; El Morsli, Mbark
2014-01-01
The effects of an electric field on the collision rates, energy exchanges and transport properties of electrons in premixed flames are investigated via solutions to the Boltzmann kinetic equation. The case of high electric field strength, which results in high-energy, non-thermal electrons, is analysed in detail at sub-breakdown conditions. The rates of inelastic collisions and the energy exchange between electrons and neutrals in the reaction zone of the flame are characterised quantitatively. The analysis includes attachment, ionisation, impact dissociation, and vibrational and electronic excitation processes. Our results suggest that Townsend breakdown occurs for E/N = 140 Td. Vibrational excitation is the dominant process up to breakdown, despite important rates of electronic excitation of CO, CO2 and N2 as well as impact dissociation of O2 being apparent from 50 Td onwards. Ohmic heating in the reaction zone is found to be negligible (less than 2% of peak heat release rate) up to breakdown field strengths for realistic electron densities equal to 1010 cm-3. The observed trends are largely independent of equivalence ratio. In the non-thermal regime, electron transport coefficients are insensitive to mixture composition and approximately constant across the flame, but are highly dependent on the electric field strength. In the thermal limit, kinetic parameters and transport coefficients vary substantially across the flame due to the spatially inhomogeneous concentration of water vapour. A practical approach for identifying the plasma regime (thermal versus non-thermal) in studies of electric field effects on flames is proposed.
Optomechanics for absolute rotation detection
NASA Astrophysics Data System (ADS)
Davuluri, Sankar
2016-07-01
In this article, we present an application of optomechanical cavity for the absolute rotation detection. The optomechanical cavity is arranged in a Michelson interferometer in such a way that the classical centrifugal force due to rotation changes the length of the optomechanical cavity. The change in the cavity length induces a shift in the frequency of the cavity mode. The phase shift corresponding to the frequency shift in the cavity mode is measured at the interferometer output to estimate the angular velocity of absolute rotation. We derived an analytic expression to estimate the minimum detectable rotation rate in our scheme for a given optomechanical cavity. Temperature dependence of the rotation detection sensitivity is studied.
Papadimitriou, Vassileios C; Spitieri, Christina S; Papagiannakopoulos, Panos; Cazaunau, Mathieu; Lendar, Maria; Daële, Véronique; Mellouki, Abdelwahid
2015-10-14
The rate coefficients for the gas phase reactions of OH radicals, k1, Cl atoms, k2, and O3, k3, with 3,3,3-trifluoro-2(trifluoromethyl)-1-propene ((CF3)2C=CH2, hexafluoroisobutylene, HFIB) were determined at room temperature and atmospheric pressure employing the relative rate method and using two atmospheric simulation chambers and a static photochemical reactor. OH and Cl rate coefficients obtained by both techniques were indistinguishable, within experimental precision, and the average values were k1 = (7.82 ± 0.55) × 10(-13) cm(3) molecule(-1) s(-1) and k2 = (3.45 ± 0.24) × 10(-11) cm(3) molecule(-1) s(-1), respectively. The quoted uncertainties are at 95% level of confidence and include the estimated systematic uncertainties. An upper limit for the O3 rate coefficient was determined to be k3 < 9.0 × 10(-22) cm(3) molecule(-1) s(-1). In global warming potential (GWP) calculations, radiative efficiency (RE) was determined from the measured IR absorption cross-sections and treating HFIB both as long (LLC) and short (SLC) lived compounds, including estimated lifetime dependent factors in the SLC case. The HFIB lifetime was estimated from kinetic measurements considering merely the OH reaction, τOH = 14.8 days and including both OH and Cl chemistry, τeff = 10.3 days. Therefore, GWP(HFIB,OH) and GWP(HFIB,eff) were estimated to be 4.1 (LLC) and 0.6 (SLC), as well as 2.8 (LLC) and 0.3 (SLC) for a hundred year time horizon. Moreover, the estimated photochemical ozone creation potential (ε(POCP)) of HFIB was calculated to be 4.60. Finally, HCHO and (CF3)2C(O) were identified as final oxidation products in both OH- and Cl-initiated oxidation, while HC(O)Cl was additionally observed in the Cl-initiated oxidation. PMID:26372403