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At least 109 records · Page 6

The nature of the bonding in the transition metal trimers

The electronic structure of the transition metal (TM) trimers was studied by comparing the bonding in the Ca3, Sc3, and Cu3 molecules. The complete active space SCF/externally contracted configuration interaction (CI) ratio for the low-lying states of Sc3 and Sc3(+) and the SCF/CI ratio for Ca3 and Cu3 trimers, all for near equilateral triangle geometries, were calculated. In addition, vertical excitation energies for Cu3 were computed, leading to a new assignment of the upper state in the resonant two-photon ionization spectrum. Based on these studies, bonding in other TM trimers was discussed.

Walch, Stephen P.↗

Free tropospheric and boundary layer measurements of NO over the central and eastern North Pacific Ocean

Reported in this paper are the Georgia Institute of Technology NO results from the fall 1983 NASA GTE/CITE 1 Airborne Field Sampling Program. These data were predominantly collected over a geographical area defined by the eastern and central North Pacific Ocean, spanning the latitude range of 15-42 deg N. These NO measurements were taken using the two-photon laser-induced fluorescence technique. The data show a general trend of increasing levels of NO from the boundary layer up to altitudes of nearly 10 km. The average midday value of NO at altitudes of less than or equal to 1.8 km was 4 parts per trillion by volume (pptv), and at about 6 km, 20 pptv, whereas that at about 9 km was 25-35 pptv, the higher value reflecting the inclusion of NO data collected from the outflow region of two electrically active cumulonimbus clouds. The high-altitude NO data strongly suggest that at least during the time of the GTE flight operation, the major sources of NO for remote regions of the Pacific Ocean were those resulting from lightning and the downward transport of stratospheric air.

Davis, D. D.↗

Partial redistribution in high-density, highly ionized plasmas

The conditions for which partial redistribution functions must be used for radiation transport in high-Z, high-density, laser-produced plasmas are examined. A previously developed two-photon formalism based on the model microfield method is used to calculate redistribution functions including electron and ion Stark broadening with ion dynamic effects. The competition between the relaxation rates and spontaneous emission is shown to determine the conditions for partial redistribution. The discussion makes use of microfield fluctuation rates and broadening coefficients which can be determined from simulation calculations. The redistribution function for the Ly-alpha transition of Ar XVIII is presented for typical plasma conditions.

Talin, B.↗

Two-photon-excited fluorescence spectroscopy of atomic fluorine at 170 nm

Two-photon-excited fluorescence spectroscopy of atomic fluorine is reported. A doubled dye laser at 286-nm is Raman shifted in H2 to 170 nm (sixth anti-Stokes order) to excite ground-state 2P(0)J fluorine atoms to the 2D(0)J level. The fluorine atoms are detected by one of two methods: observing the fluorescence decay to the 2PJ level or observing F(+) production through the absorption of an additional photon by the excited atoms. Relative two-photon absorption cross sections to and the radiative lifetimes of the 2D(0)J states are measured.

Herring, G. C.↗

CH(A, B-X) fluorescence from vacuum ultraviolet excitation of CH3

The fluorescence due to single-photon and two-photon excitation of CH3 produced by the reaction of CH4 with F or Cl in a flow tube is investigated experimentally. The excitation source is an excimer laser operating with pulse duration 6 nsec and repetition rate 20 Hz, and the fluorescence is observed using a 0.25-m spectrometer and a 1024-channel diode array; the results are presented graphically. Emission is detected at 157 nm (with approximate cross section 8 x 10 to the -19th sq cm) and 193 nm, but not at 248 nm. The applicability of these data to studies of hydrocarbon combustion, the methane oxidation cycle in the atmosphere, interstellar molecule formation, and diamond film fabrication is indicated.

Ye, Chao↗

Time-resolved laser-induced fluorescence of selected even-parity 7p states of Xe I

Lifetimes and self-quenching rates have been measured for excited states of Xe I that were populated using simultaneous two-photon absorption. Lifetimes measured in this study are somewhat shorter than those measured using the broadband-excitation technique. Lifetimes reported here are all faster than 100 nsec. Deactivation rates are approximately 2 x 10 to the -10th cu cm/sec per mol.

Mcgee, T. J.↗

Fluorescence from photoexcitation of C2H2 at 50-106 nm

The photoabsorption and fluorescence cross sections of C2H2 were measured in the 50-106 nm region using synchrotron radiation as a light source. Fluorescence observed at several excitation wavelengths was dispersed to identify the fluorescing species that are excited C2H, C2, CH, H, and possibly C2H2. The photodissociation process of C2H2 leading to the formation of fluorescing species is discussed. The C2 (C-A) emission observed at 92.3 and 95.5 nm is produced by the molecular elimination process associated with superexcited state(s). Fluorescence spectra from the two-photon excitation of C2H2 at 157.5 and 193 nm were also observed and compared with those of single-photon excitation at the equivalent excitation energies.

Han, J. C.↗

Fast molecular shocks. I - Reformation of molecules behind a dissociative shock

The physical and chemical processes that operate in the cooling gas behind a fast, dissociative, single-fluid shock propagating in a dense interstellar cloud are discussed. The treatment extends previous theoretical work on fast molecular shocks by including the effects of the conversion of Ly-alpha photons into radiation of the two-photon continuum and into H2 Lyman band emission lines, the effects of CO photodissociation following line absorption, and the formation and destruction of molecules containing the elements nitrogen, silicon, and sulphur, and of the complex hydrocarbons. Abundance profiles for the molecular species of interest are presented. After molecular hydrogen begins to reform, by means of gas phase and grain surface processes, the neutral species OH, H2O, O2, CO, CN, HCN, N2, NO, SO, and SiO reach substantial abundances. The molecular ions HeH(+), OH(+), SO(+), CH(+), H2(+), and H3(+), are produced while the gas is still hot and partially ionized. Emissions from them provide a possible diagnostic probe of fast molecular shocks.

Neufeld, David A.↗

On the electron affinity of Au3

The EA of Au3 is estimated to be 3.93 eV. The calculations also show that the feature in the photodetachment spectrum at about 2 eV electron binding energy is due to a two-photon process involving fragmentation of Au3(-) to Au and Au2(-) and subsequent photodetachment of Au2(-). Au3 is found to have a 2B2 ground state that is only slightly distorted from an equilateral triangle.

Bauschlicher, Charles W., Jr.↗

Positron annihilation in gamma-ray bursts

Emission features appear at energies of 350 to 450 keV in the spectra of a number of gamma ray burst sources. These features were interpreted as electron-positron annihilation lines, redshifted by the gravitational field near the surface of a neutron star. Evidence that gamma ray bursts originate at neutron stars with magnetic field strengths of approx. 10(exp 12) Gauss came from recent observations of cyclotron scattering harmonics in the spectra of two bursts. Positrons could be produced in gamma ray burst sources either by photon-photon pair production or by one-photon pair production in a strong magnetic field. The annihilation of positrons is affected by the presence of a strong neutron star magnetic field in several ways. The relaxation of transverse momentum conservation causes an intrinsic broadening of the two-photon annihilation line and there is a decrease in the annihilation cross section below the free-space value. An additional channel for one-photon annihilation also becomes possible in high magnetic fields. The physics of pair production and annihilation near strongly magnetized neutron stars will be reviewed. Results from a self-consistent model for non-thermal synchrotron radiation and pair annihilation are beginning to identify the conditions required to produce observable annihilation features from strongly magnetized plasmas.

Harding, Alice K.↗

H2/O2 three-body rates at high temperatures

The extraction of thrust from air breathing hypersonic propulsion systems is critically dependent on the degree to which chemical equilibrium is reached in the combustion process. In the combustion of H2/Air mixtures, slow three-body chemical reactions involving H-atoms, O-atoms, and the OH radical play an important role in energy extraction. A first-generation high temperature and pressure flash-photolysis/laser-induced fluorescence reactor was designed and constructed to measure these important three-body rates. The system employs a high power excimer laser to produce these radicals via the photolysis of stable precursors. A novel two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical thickness or O2 absorption problems. To demonstrate the feasibility of the technique the apparatus in the program is designed to perform preliminary measurements on the H + O2 + M reaction at temperatures from 300 to 835 K.

Marinelli, William J.↗

Picosecond pulse measurements using the active laser medium

A simple method for measuring the pulse lengths of synchronously pumped dye lasers which does not require the use of an external nonlinear medium, such as a doubling crystal or two-photon fluorescence cell, to autocorrelate the pulses is discussed. The technique involves feeding the laser pulses back into the dye jet, thus correlating the output pulses with the intracavity pulses to obtain pulse length signatures in the resulting time-averaged laser power. Experimental measurements were performed using a rhodamine 6G dye laser pumped by a mode-locked frequency-doubled Nd:YAG laser. The results agree well with numerical computations, and the method proves effective in determining lengths of picosecond laser pulses.

Bernardin, James P.↗

An intercomparison of airborne nitrogen dioxide instruments

Results on NO2 instruments are reported from the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986. The instruments tested were (1) a two-photon LIF system using a laser for NO2-NO photolysis, (2) a chemiluminescence (CL) detector using FeSO4 for NO2-NO conversion, (3) a CL detector using an arc lamp for NO2-NO photolysis, and (4) a tunable-laser-diode multipath-absorption system. The procedures for the CITE 2 ground-based and flight tests are described in detail, and the results are presented in extensive graphs. Instrument (2) was eliminated because the FeSO4 converted atmospheric PAN to NO, resulting in spuriously high NO2 values. The remaining instruments gave readings in 30-40-percent agreement at NO2 mixing ratios of 100-200 parts per trillion by volume (pptv). At ratios below 50 pptv, the correlation among the measurements was very poor, with a tendency for system (4) to give higher values than (1) or (3).

Gregory, G. L.↗

An intercomparison of airborne nitric oxide measurements - A second opportunity

Results are reported from a comparison of three tropospheric NO measurement instruments during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) in summer 1986. The instruments tested were those used in CITE 1 (Hoell et al., 1987): a two-photon LIF system and two chemiluminescence systems. It is found that the mixing ratios obtained with the three systems agreed to within 15-20 parts per trillion volume (pptv) for sampling perods of 1-6 min at mixing ratios less than 20 pptv; the average difference between pairs of measurements was 5-7 pptv, which is considered to be the uncertainty in state-of-the-art ambient NO measurements.

Gregory, Gerald L.↗

Observed and model-calculated NO2/NO ratios in tropospheric air sampled during the NASA GTE/CITE-2 field study

Airborne measurements of NO2/NO ratios in the free troposphere, obtained using two-photon LIF (TP-LIF) and chemiluminescence (CL) detectors during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986, are analyzed and compared with the predictions of a photochemical model. The derivation of the model is outlined, with an emphasis on the role of peroxy radicals in the fast photochemical cycling of NO and NO2 and the production of O3; the CITE 2 instruments and flight protocols are described; and the results are presented in extensive tables and graphs and discussed in detail. It was found that on three CITE 2 flights the CL data were systematically greater than the TP-LIF data; when these data were removed, the averaged values of the two instruments agreed to within 1 percent. The NO2/NO ratios predicted by the model are shown to be consistent with the measurements, although usually 20-25 percent lower.

Chameides, W. L.↗

On the observability of the gamma-ray line flux from dark matter annihilation

The limits on the possible cosmic gamma-ray line flux from the two-photon annihilation of dark matter in the Galaxy are discussed. These limits are derived using both particle physics and cosmological constraints on dark matter candidates which arise in supersymmetric extensions of the standard model of particle physics. Results are given in terms of allowed and prescribed areas in the flux-energy plane. Then these bounds are used to consider the observability of the line flux above continuum background fluxes using future high-resolution gamma-ray telescopes.

Rudaz, S.↗

Quantitative determination of H2, HD, and D2 internal-state distributions by (2+1) resonance-enhanced multiphoton ionization

Results are presented of an experimental study of (2+1) resonance-enhanced multiphoton ionization (REMPI) detection of H2, HD, and D2 via the E,F two-photon transition, in which the relationship between ion signals and quantum-state populations was determined by calibration against a thermal effusive source. Vibrational and rotational correction factors were obtained for 102 rovibrational levels for v-double-prime = 0, 1, and 2 and for J-double-prime ranging from 0 to 17. These correction factors make it possible to convert ion signals into relative quantum-state populations without relying on a theoretical description of the (2+1) REMPI process.

Rinnen, Klaus-Dieter↗

H2/O2 three-body rates at high temperatures

Hydrogen atoms are produced in the presence of excess O2, and the first-order decay are studied as a function of temperature and pressure in order to obtain the rate coefficient for the three-body reaction between H-atoms and O2. Attention is focused on the kinetic scheme employed as well as the reaction cell and photolysis and probe laser system. A two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical-thickness or O2-absorption problems. Results confirm measurements reported previously for the H + O2 + N2 reaction at 300 K and extend these measurements to higher temperatures. Preliminary data indicate non-Arrehenius-type behavior of this reaction rate coefficient as a function of temperature. Measurements of the rate coefficient for H + O2 + Ar reaction at 300 K give a rate coefficient of 2.1 +/- 0.1 x 10 to the -32nd cm exp 6/molecule sec.

Marinelli, William J.↗