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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry

Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes are understood. It has been shown that photolysis of nitrate in the snowpack plays a major role in nitrate loss and that the photolysis products have a significant influence on the local troposphere as well as on other species in the snow. Reported quantum yields for the main reaction spans orders of magnitude – apparently a result of whether nitrate is located at the air-ice interface or in the ice matrix – constituting the largest uncertainty in models of snowpack NO{sub x} emissions. Here, a laboratory study is presented that uses snow from Dome C and minimizes effects of desorption and recombination by flushing the snow during irradiation with UV light. A selection of UV filters allowed examination of the effects of the 200 and 305 nm absorption bands of nitrate. Nitrate concentration and photon flux were measured in the snow. The quantum yield for loss of nitrate was observed to decrease from 0.44 to 0.003 within what corresponds to days of UV exposure in Antarctica. The superposition of photolysis in two photochemical domains of nitrate in snow is proposed: one of photolabile nitrate, and one of buried nitrate. The difference lies in the ability of reaction products to escape the snow crystal, versus undergoing secondary (recombination) chemistry. Modeled NO{sub x} emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ∼1%, much lower than reported for aqueous chemistry. A companion paper presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

A flash photolysis-resonance fluorescence study of the formation of O/1D/ in the photolysis of water and the reaction of O/1D/ with H2, Ar, and He

The technique employed in the study utilizes the vacuum ultraviolet flash photolysis of H2O combined with time resolved, simultaneous detection of H and O via resonance fluorescence at 121.6 and 130.2 nm respectively. The measurements were made by means of photon counting and multichannel scaling. The sensitivity of the system for H and O is discussed. Experiments are reported in which signals due to H and O were accumulated from the flash photolysis of a mixture of 0.1 torr H2O and 100 torr Ar. Attention is given to the relative importance of two primary processes in the photolysis of water.

Stief, L. J.↗
DOE OSTI2019

Photolysis of Tp'Rh(CNneopentyl)(PhNCNneopentyl) in the presence of ketones and esters: kinetic and thermodynamic selectivity for activation of different aliphatic C–H bonds

The competitive fragment [Tp'Rh(CNneopentyl)], generated from the precursor Tp'Rh(CNneopentyl)(PhN CNneopentyl), underwent oxidative addition of substituted ketones and esters resulting in Tp'Rh(CNneopentyl)(R)(H) complexes (Tp' = tris-(3,5-dimethylpyrazolyl)borate). These C–H activated complexes underwent reductive elimination at varying temperatures (24–70 °C) in C 6 D 6 or C 6 D 12 . Using previously established kinetic techniques, the relative Rh–C bond strengths were calculated. Analysis of the relative Rh–C bond strengths vs. C–H bond strengths demonstrates a linear correlation with slope R M–C/C–H = 1.22 (12). In general, α-substituents increase the relative Rh–C bond strengths compared to the C–H bond that is broken.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

A flash photolysis-resonance fluorescence study of the formation of O(D-1) in the photolysis of water and reaction of O(D-1) with H2, Ar and He

The relative importance of two primary processes in the photolyis of water: (1) H2O + h (nu) yields H + OH, and (2) H2O + h (nu) yields H2 + OD-1 were determined in a direct manner by time resolved detection (via resonance fluorescence) of H and O formed in processes 1 and 2 respectively. The initially formed OD-1 was deactivated to ground state OP-3 prior to detection via resonance fluorescence. The relative quantum yields for processes 1 and 2 are 0.89 and 0.11 for the wavelength interval 105 to 145nm and = to or greater than 0.99, and = to or less than 0.01 for the wavelength interval 145 to 185nm. Rate constants at 300 K for the reactions OD-1 + H2, + Ar, and + He are presented.

Stief, L. J.↗
NASA NTRS1996

Pressure-Dependent Yields and Product Branching Ratios in the Broadband Photolysis of Chlorine Nitrate

The photolysis of chlorine nitrate was studied using broadband flash photolysis coupled with long-path ultraviolet-visible absorption spectroscopy. Branching ratios for the Cl + NO3 and ClO + NO2 product channels were determined from time-dependent measurements of ClO and NO3 concentrations. Yields of the ClO and NO3 products displayed a dependence on the bath gas density and the spectral distribution of the photolysis pulse. Product yields decreased with increasing bath gas density regardless of the spectral distribution of the photolysis pulse; however, the decrease in product yield was much more pronounced when photolysis was limited to longer wavelengths. For photolysis in a quartz cell (lambda > 200 nm) the yield decreased by a factor of 2 over the pressure 10-100 Torr. In a Pyrex cell (lambda > 300 nm), the yield decreased by a factor of 50 over the same pressure range. When photolysis was limited to lambda > 350 nm, the yield decreased by a factor of 250. Branching ratios for the photolysis channels [ClONO2 + h.nu yields ClO + NO2 (1a) and ClONO2 + h.nu yields Cl + NO3 (lb)] were determined from the relative ClO and NO3 product yields at various pressures. Although the absolute product yield displayed a pressure dependence, the branching between the two channels was independent of pressure. The relative branching ratios (assuming negligible contributions from other channels) are 0.61 +/- 0.20 for channel 1a and 0.39 +/- 0.20 for channel lb for photolysis with lambda > 200 nm and 0.44 +/- 0.08 for channel 1a and 0.56 +/- 0.08 for channel 1b for photolysis with lambda > 300 nm. The implications of these results for the chemistry of the lower stratosphere are discussed.

Nickolaisen, Scott L.↗
DOE OSTI2015

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

This paper presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry–climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C 12 and C 16 n-alkane reactions with OH at low and high NO x . Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NO x ) to ~45 % (high NO x ) for α-pinene, ~15 % for toluene, ~25 % for C 12 n-alkane, and ~10 % for C 16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C 16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA photolysis rate of J SOA = 4 × 10 −4 J NO 2 . Modeling results indicate that this photolytic loss rate would decrease SOA mass by 40–60 % for most species after 10 days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle and thus the quantity of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales of less than 7 days that are comparable to wet deposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photolysis Controls Atmospheric Budgets of Biogenic Secondary Organic Aerosol

Secondary organic aerosol (SOA) accounts for a large fraction of tropospheric particulate matter. While SOA production rates and mechanisms have been extensively investigated, loss pathways remain uncertain. Most large-scale chemistry and transport models account for mechanical deposition of SOA, but not chemical losses, such as photolysis. There is also a paucity of laboratory measurements of SOA photolysis, which limits how well photolytic losses can be modeled. Here we show, through a combined experimental and modeling approach, that photolytic loss of SOA mass significantly alters SOA budget predictions. Using environmental chamber experiments, we find that SOA produced from several biogenic volatile organic compounds (VOCs) undergoes photolysis-induced mass loss at rates between 0 and 2.2% ± 0.4% of nitrogen dioxide (NO 2 ) photolysis, equivalent to average atmospheric lifetimes as short as 10 hours. We incorporate our photolysis rates into a regional chemical transport model to test the sensitivity of predicted SOA mass concentrations to photolytic losses. The addition of photolysis at rates consistent with our experimental conditions causes a ~50% reduction in biogenic SOA loadings over the Amazon, indicating that photolysis exerts a substantial control over the atmospheric SOA lifetime, with a likely dependence upon SOA molecular composition and thus production mechanisms.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

HO<sub><i>x</i></sub> and NO<sub><i>x</i></sub> production in oxidation flow reactors via photolysis of isopropyl nitrite, isopropyl nitrite-d<sub>7</sub>, and 1,3-propyl dinitrite at <i>λ</i> = 254, 350, and 369 nm

Abstract. Oxidation flow reactors (OFRs) are an emerging technique for studying the formation and oxidative aging of organic aerosols and other applications. In these flow reactors, hydroxyl radicals (OH), hydroperoxyl radicals (HO2), and nitric oxide (NO) are typically produced in the following ways: photolysis of ozone (O3) at λ=254 nm, photolysis of H2O at λ=185 nm, and via reactions of O(1D) with H2O and nitrous oxide (N2O); O(1D) is formed via photolysis of O3 at λ=254 nm and/or N2O at λ=185 nm. Here, we adapt a complementary method that uses alkyl nitrite photolysis as a source of OH via its production of HO2 and NO followed by the reaction NO + HO2 → NO2 + OH. We present experimental and model characterization of the OH exposure and NOx levels generated via photolysis of C3 alkyl nitrites (isopropyl nitrite, perdeuterated isopropyl nitrite, 1,3-propyl dinitrite) in the Potential Aerosol Mass (PAM) OFR as a function of photolysis wavelength (λ=254 to 369 nm) and organic nitrite concentration (0.5 to 20 ppm). We also apply this technique in conjunction with chemical ionization mass spectrometer measurements of multifunctional oxidation products generated following the exposure of α-Pinene to HOx and NOx obtained using both isopropyl nitrite and O3 + H2O + N2O as the radical precursors.

Meteorology & Atmospheric Sciences↗
NASA NTRS1978

Synchronized flash photolysis and pulse deposition in matrix isolation experiments

An apparatus is described which permits flash photolysis of a pulse-deposited gas mixture in a matrix isolation experiment. This technique obviates the limitations of in situ photolysis imposed by the cage effect and by secondary photolysis. The matrix is deposited in pulses at 30-s intervals and photolyzed sequentially by four synchronized flashlamps approximately 1 ms before the pulse strikes the cold surface. Pulsed deposition maintains adequate isolation and causes line narrowing, which enhances spectral sensitivity. The efficacy of flash photolysis combined with pulsed deposition for producing and trapping transient species was demonstrated by infrated detection of CF3 (from photolysis of CF3I/Ar mixtures) and of ClCO (from photolysis of Cl2/CO/Ar mixtures). The apparatus was used to study the photolytic decomposition of gaseous tricarbonylironcyclobutadiene, C4H4Fe(CO)3. The results indicate that the primary photolytic step is not elimination of C4H4, as suggested earlier, but rather of CO.

Allamandola, Louis J.↗
DOE OSTI2018

Reliable hydrogen production from methanol photolysis in aqueous solution by a harmony between In and Zn in bimetallic zinc indium sulfide

Highlights: • Band-gaps in Zn{sub x}In{sub y}S{sub z} particles were shorten. • Hydrogen production by methanol photolysis was the best on ZnInS{sub 2.5}. • Recombination between electrons and holes during methanol photolysis became long on ZnInS{sub 2.5}. - Abstract: This study focuses on hydrogen production by methanol photolysis using zinc indium sulfide (Zn{sub x}In{sub y}S{sub z}). The X-ray diffraction identified that the synthesized Zn{sub 2}InS{sub 2.5} and ZnInS{sub 2.5} particles have a hexagonal Zn{sub 3}In{sub 2}S{sub 6} structure, but when In of twice amount against Zn is coexisted, the particle exhibits a perfect hexagonal ZnIn{sub 2}S{sub 4} structure. The results in ultra-violet absorption and X-ray photoelectron spectroscopy analysis confirmed that the band-gaps of Zn{sub x}In{sub y}S{sub z} particles decrease depend on the coexistence of In. However, the photocurrent which related to the life time of excited electrons was no correlation with the Zn/In molar ratio, and it was the highest on ZnInS{sub 2.5} particle with a ratio of Zn:In = 1:1. Eventually, the hydrogen production by methanol photolysis in aqueous solution was the best on ZnInS{sub 2.5} particle. This result gives ultimately relevant that the recombination between electrons and holes during methanol photolysis could be suppressed on bimetallic ZnInS{sub 2.5} particle.

36 MATERIALS SCIENCE↗
NASA NTRS1995

Pressure Dependence and Metastable State Formation in the Photolysis of Dichlorine Monoxide (Cl2O)

Physics%K photolysis, dichlorine monoxide, pressure%U http://techreports.jpl.nasa.gov/1995/95-0924.pdfThe photodissociation of dichlorine monoxide (Cl2O) was studied using broadband flash photolysis to investigate the influence of variations in the photolysis wavelength domain, bath gas pressure, and bath gas identity on the yield and temporal dependence of the ClO product. ClO yields were independent of bath gas pressure when the photolysis spectral band extended to 200 nm (quartz cutoff) but for photolysis restricted to wavelengths longer than about 250 nm, ClO yields decreased with increasing bath gas pressure and there was a pressure-dependent delay in the formation of ClO.!.

photolysis↗
DOE OSTI2017

Mechanism of Ferric Oxalate Photolysis

Iron(III) oxalate, Fe 3+ (C 2 O 4 ) 3 3– , is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO 2 is not well understood for any system. Here, we employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D 2 O and H 2 O up to 3 ns following photoexcitation. We find that intramolecular electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO 2 (aq) and a species inferred to be CO 2 •– based on the appearance of a new vibrational absorption band and ab initio simulation. Our work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Photolysis rates based on Schumann-Runge band approximations and irradiance measurements

The photolysis rate (J3) for CF2Cl2(F-12) in the stratosphere has been computed for three altitudes using measured solar fluxes from a balloon borne spectrometer. The rate is compared with that obtained by computing the attenuated flux using effective cross sections appropriate for the Schumann-Runge bands (J1) (Allen and Frederick, 1982). The result shows that the error in the F-12 photolysis rate caused by using the Allen and Frederick approximation is about 10 percent (J1 less than J3) for altitudes between 32 and 38 km with solar zenith angles less than about 62 degrees. For species other than O2, this implies that the discrepancy in photolysis rates associated with the Schumann-Runge band approximations are not likely to be important. Within the Schumann-Runge band region the computed errors for F-12 photolysis are about 10.5 percent at 38.13 km and increase with decreasing altitude. If this error applies to O2 photolysis, there may be the possibility of an incorrect calculation of net odd oxygen production in photochemical models.

Herman, J. R.↗
DOE OSTI2014

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. [“Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry,” J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ({sup 15}N, {sup 17}O, and {sup 18}O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ{sup 15}N, δ{sup 18}O, and Δ{sup 17}O). From these measurements an average photolytic isotopic fractionation of {sup 15}ε = (−15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of {sup 15}ε = (−47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from −40 to −74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of {sup 14}NO{sub 3}{sup −} and {sup 15}NO{sub 3}{sup −} in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well reproduced the values obtained in the laboratory study. These cross sections can be used in isotopic models to reproduce the stable isotopic composition of nitrate found in Antarctic snow profiles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Laboratory simulations of PH3 photolysis in the atmospheres of Jupiter and Saturn

The effects of pressure, temperature, light wavelength and intensity, and components of the atmosphere of the Jovian planets on the photolysis of PH3 were experimentally studied. The products of the photolysis, P2H4 and red phosphorus, exhibited little variation when the irradiation experiments were performed under conditions prevalent in Jupiter's atmosphere. No quenching of PH2 radicals by the levels of hydrocarbons present in the Jovian atmosphere was noted. The high partial pressure of hydrogen present on Jupiter should have no effect on the course of the photolysis. The low temperatures on Jupiter and Saturn may result in some condensation of P2H4, but P2H4 had sufficient vapor pressure in the experimental studies at 157 K to be slowly converted to red phosphorus. The products of PH3 photolysis were the same whether a 147, 184.9, or 206.2 nm monochromatic light source or a xenon lamp with a broad spectral output was used.

Ferris, J. P.↗
NASA NTRS2002

Investigation of N2O Production from 266 and 532 nm Laser Flash Photolysis of O3/N2/O2 Mixtures

Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and they appear to be the first suggested photochemical mechanism that is capable of explaining the altitude dependence of the observed mass -independent isotopic signature.

Estupinan, E. G.↗
DOE OSTI2023

Kinetic study of the azo – Hydrazone photoinduced mechanism in complexes with a -Re(CO) 3 L 0/+ core by flash photolysis

The photoprocesses of three rhenium(I) tricarbonyl complexes, fac-Re(NN)(CO) 3 L 0/+ , bearing an azo/hydrazone ligand, NN, and L = Cl, Br or CH 3 CN as axial ligand, were studied by time-resolved spectroscopic techniques. Flash irradiation of deaerated solutions of the complexes in acetonitrile photogenerated intermediates with intense optical absorptions in the UV–vis spectral region of the hydrazone ligand. The decay of the intermediates photogenerated with the Cl, Br and CH 3 CN ligands in the axial position proceeds by three different mechanisms. For the fac-Re(NN)(CO) 3 Cl, a three-step mechanism involving isomerization, tautomerization and rotation accounts for the spectroscopic transformations. In contrast to the flash photolysis result, the continuous photolysis of the complex in acetonitrile does not show spectroscopic changes associated with the generation of a stable product, i.e., the complex exhibits a photoreversible behavior. The first step observed in the flash irradiation of fac-Re(NN)(CO) 3 Cl, is missing in the decay of the photogenerated intermediates with fac-Re(NN)(CO) 3 Br and fac-[Re(NN)(CO) 3 CH 3 CN] + . A possible reason for this absence is that the process is too fast for the time-response of the flash photolysis set-up. Time-resolved spectra and associated reaction rate data for the Re(I) complexes are communicated and discussed. Finally, DFT calculations support a plausible E → Z mechanism with thermal back-isomerization mediated by tautomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗