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The reaction of O(3P) with 1-C4H8 was examined in the presence of CO which scavenges HO radicals to produce CO2. From the CO2 quantum yield, an upper limit to the efficiency of HO production in the reaction of O(3P) with 1-C4H8 was found to be 0.020 at both 298 and 473 K.
The parameters for a chemical technique can be outlined from the following set of desirable goals: (1) sufficient conversion of tracer species A to product B that B can be measured quantitatively in the presence of A and a great excess of air; (2) specificity of reaction such that A is converted to B only by reaction with HO; and (3) sufficient sensitivity for detection that the ambient concentration of HO is not seriously perturbed by the presence of A and B. This proposed study involves finding a chemical reaction specific enough for OH, and a measurement of the product formed. What one wants is a rate constant of about 10 to the -10th power cu cm/s, so that 0.1 percent of the OH will be converted in 100 s. Laboratory studies are needed to find a reaction which will fill this bill, yielding a product in quantity sufficient for precise measurement. This is an extremely fast constant and the search may be difficult. Again there is a question of perturbing the local environment, while still providing a sensitive measurement. Also the temperature and pressure dependence of the reaction rate is a complicated function for many of these species (that is, one must use a RRKM or Troe-based picture), and must be taken into account.
The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.
Longitudinal pumping by laser diodes increases efficiency. Improved holmium:yttrium lithium fluoride laser radiates as much as 56 mW of power at wavelength of 2.1 micrometer. New Ho:YLF laser more compact and efficient than older, more powerful devices of this type. Compact, efficient Ho:YLF laser based on recent successes in use of diode lasers to pump other types of solid-state lasers.
Solid-state lasers pumped by continuous-wave diode lasers can be Q-switched to obtain high peak power output pulses. The dependence of laser-pulse energy, average output power, peak power, and pulse width on pulse-repetition frequency in Q-switched Nd:YAG and Ho:YLF lasers is determined and compared. At low pulse repetition rates, the much longer upper-stage lifetime in Ho:YLF gives a distinct advantage. At higher pulse rates, the overall laser efficiency and the stimulated emission cross section are more important parameters, leading to an advantage for Nd:YAG. The results are of significance for designing lasers for use in space optical communications and remote sensing systems.
The energy transfer processes in Tm,Ho:YAG lasers were investigated in spectral studies and measurements of the temporal response to pulsed excitation. These processes include the population of the 3H4 pump band of Tm, cross-relaxation in Tm, the transfer of energy from Tm to Ho, and various loss mechanisms. It was found that the Tm cross-relaxation is due to a dipole-dipole interaction between Tm ions and that the rate of this process is a function of temperature and ion concentration.
The development of eye-safe, solid-state Lidar systems is discussed, with an emphasis on Coherent Doppler Lidar for Atmospheric Wind Measurements. The following subject areas are covered: tunable Ho DIAL (Differential Absorption Lidar)/lidar atmospheric measurements; atmospheric turbulence measurements and detector arrays; diurnal measurements of C(sub n)(sup 2) for KSC lidar measurements; and development of single-frequency Ho laser/lidar.
In recent advanced lasers, 2 micron solid-state lasers such as Tm:YAG and Ho:YAG lasers are very attractive for laser radar remote sensing technologies because of eye safety, realizations of all solid-state laser pumped by diode laser and smaller dimension, tunability of lasing wavelength, possibility of coherent detection, etc. Featuring these advantages, 2 micron lasers have been candidated as laser transmitters for use in water vapor Differential Absorption Lidar (DIAL), laser altimeter, Doppler wind sensor, Mie lidar, etc. Characterization of a tunable Cr, Tm, Ho:YAG laser and its applications to spectroscopy concerning absorption and reflectance are reported.
Unique features include high efficiency and tunability at wavelengths near 2.067 micrometers. Continuous-wave, diode-pumped Tm,Ho:YLF laser tuned by tilting Fabry-Perot etalon and/or adjusting temperature of Tm,Ho:YLF crystal. Proposed for use in remote sensing of winds and in remote sensing of CO2 and H2O, of which many strong absorption lines over-lap laser tuning range. Range extended by tuning to wave-length between CO2 and H2O absorption peaks.
We present the emitter efficiency results for the thin film 25 percent Ho YAG (Yttrium Aluminum Garnet, Y3Al5O12) selective emitter from 1000 to 1700 K with a platinum substrate. Spectral emittance and emissive power measurements were made (1.2 less than lambda less than 3.2 microns) and used to calculate the radiative efficiency. The radiative efficiency and power density of rare earth doped selective emitters are strongly dependent on temperature and experimental results indicate an optimum temperature (1650 K for Ho YAG) for thermophotovoltaic (TPV) applications.
Tuning of both the pump laser, a Ho:Tm:YLF laser operating on the 5 I 7 - 5 I 8 transition, and an AgGaSe2 parametric oscillator has been demonstrated. Tuning of the Ho:Tm:YLF laser is complicated but not frustrated by the existence of both CO2 and H2O lines in the vicinity of the laser transition. Tuning of the parametric oscillator was achieved by tuning of the pump laser. Injection seeding of the parametric oscillator on the nonresonant signal was also demonstrated. In addition, the measured efficiencies of the parametric oscillator were compared by two different methods, measuring the parametric-oscillator output energy and measuring the energy depleted from the pump. By comparison of these measurements, the intrinsic efficiency of the parametric oscillator cab be determined
An optical efficiency of 0.052 under normal mode operation for diode-pumped Ho:Tm:YLiF4 at a pulse repetition frequency of 10 Hz has been achieved. Laser output energy of 30 mJ in single Q-switched pulses with 600-ns pulse length were obtained for an input energy of 3 J. A diffusion-bonded birefringent laser rod consisting of Ho:Tm-doped and undoped pieces of YLF was utilized for 10-Hz operation.
SONEX, which was delayed by aircraft inspection problems, began the second week of October and concluded in mid-November with 16 flights. These flights covered the Pacific Ocean off the western United States, transits across the United States, the western coast of Europe, and the North and Central Atlantic Ocean. Particular attention was paid to the North Atlantic Flight Corridor. ATHOS collected high-quality HO(x) data on 15 flights. Observations taken at 5 Hz were typically averaged into 20-second measurements. Each 20-second measurement has precision 1(sigma) of less than 0.01 pptv. OH measurements were generally made from the surface to flight altitudes. HO2 measurements, which require reagent NO flow, were made from flight altitudes to near the top of the planetary boundary layer. Measured OH and HO2 during SONEX was generally lower than the measured OH and HO2 during SUCCESS (April-May, 1996, central United States). Whereas during SUCCESS midday OH was 0.1-0.5 pptv and HO2 was 3-15 pptv, during SONEX midday OH was 0.02-0.2 pptv and HO2 was 0.5-8 pptv. Part of this difference results from the midday solar zenith angles, which were larger during SONEX than during SUCCESS due to both the season and the generally higher latitudes sampled during SONEX. However, some of the difference may be due to differences in HOx sources, since less air influenced by convection was sampled during SONEX. These possibilities await post-flight calibrations of ATHOS and analysis of observations of HO(x) and simultaneously measured meteorology and trace species.
Space based coherent lidar for global wind measurement requires an all solid state laser system with high energy, high efficiency and narrow linewidth that operates in the eye safe region. A Q-switched, diode pumped Ho:Tm:YLF 2 micrometer laser with output energy of as much as 125 mJ at 6 Hz with an optical-to-optical efficiency of 3% has been reported. Single frequency operation of the laser was achieved by injection seeding. The design of this laser is being incorporated into NASA's SPARCLE (SPAce Readiness Coherent Lidar Experiment) wind lidar mission. Laser output energy ranging from 500 mJ to 2 J is required for an operational space coherent lidar. We previously developed a high energy Ho:Tm:YLF master oscillator and side pumped power amplifier system and demonstrated a 600-mJ single frequency pulse at a repetition rate of 10 Hz. Although the output energy is high, the optical-to-optical efficiency is only about 2%. Designing a high energy, highly efficient, conductively cooled 2-micrometer laser remains a challenge. In this paper, the preliminary result of an end-pumped amplifier that has a potential to provide a factor 3 of improvement in the system efficiency is reported.
Establishing a quantitative understanding of the abundance of peroxynitric acid (HNO4) is of interest because the reaction of OH with HNO4 is believed to be a significant sink for HO(x) in the lower stratosphere and upper troposphere. We present concentration profiles of KNO4 obtained by the MkIV Fourier transform infrared spectrometer using the solar occultation technique during two flights, one at 35 N on 25 September 1993 (930925) and the other near 66 N on 7 May 1997 (970507). The observations of HN04 present an apparent dilemma: the calculated profile for HNO4 found using standard kinetics is in relatively good agreement with the mid-latitude observations, but the calculated profile for HNO4 found using the same kinetics overestimates the high-latitude summer observations by nearly a factor of two. Resolution of this dilemma is the focus of our investigation. We show that introduction into our photochemical model of a speculative long-wave (lambda greater than 650 nm) photolytic pathway for HNO4 leads to good agreement between theory and observation of HN04 for both the mid-latitude and high-latitude regions. Implications for the budget of HO(x) are also discussed.
Ho:Tm:Er:LuAG demonstrated simultaneous laser oscillation associated with two different transitions and different atoms. Two wavelength oscillation, or TWO, can be achieved in a single laser and single resonator. Moreover, the wavelength can be electronically controlled by varying the pump pulse length, Either the short wavelength, the Ho (5)1(sub 7) to (5)1(sub 8) transition at 2.1 microns, or the long wavelength, the Er (4)1(sub 11/2) to (4)1(sub 13/2) transition at 2.7 microns, or both wavelengths simultaneously can be produced without resorting to mechanical intervention. Consequently, a single laser system can easily switch between producing either of these useful wavelengths. Laser operation of both transitions has been characterized and is presented.
A room temperature solid-state laser is provided. A laser crystal is disposed in a laser cavity. The laser crystal has a LuAG host material doped with a concentration of about 0.35% Ho ions, about 5.57% Tm ions and at least about 1.01% Cr ions. A broadband energizing source such as a flashlamp is disposed transversely to the laser crystal to energize the Ho ions, Tm ions and Cr ions.
The development of materials and fabrication technology for field-controlled spectrally active optics is essential for applications such as membrane optics, filters for LIDARs, windows for sensors, telescopes, spectroscopes, cameras and flat-panel displays. The dopants of rare earth elements, in a host of optical systems, create a number of absorption and emission band structures and can easily be incorporated into many high quality crystalline and amorphous hosts. In wide band-gap semiconductors like ScN, the existing deep levels can capture or emit the mobile charges, and can be ionized with the loss or capture of the carriers which are the fundamental basis of concept for smart optic materials. The band gap shrinkage or splitting with dopants supports the possibility of this concept. In the present work, a semi-metallic material (ScN) was doped with rare earth elements (Er, Ho) and tested under an applied electric field to characterize spectral and refractive index shifts by either Stark or Zeeman Effect. These effects can be verified using the UV-Vis spectroscopy, the Hall Effect measurement and the ellipsometric spectroscopy. The optical band gaps of ScN doped with Er and doped with Ho were experimentally estimated as 2.33eV and 2.24eV ( 0.2eV) respectively. This is less than that of undoped ScN (2.5 0.2eV). The red-shifted absorption onset is a direct evidence for the decrease of band gap energy (Eg), and the broadening of valence band states is attributable to the doping cases. A decrease in refractive index with an applied field was observed as a small shift in absorption coefficient using a variable angle spectroscopic ellipsometer. In the presence of an electric field, mobile carriers are redistributed within the space charge region (SCR) to produce this electro-refractive effect. The shift in refractive index is also affected by the density and location of deep potential wells within the SCR. In addition, the microstructure change was observed by a TEM analysis. These results give an insight for future applications for the field-controlled spectrally active material systems.