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At least 1,009 records · Page 56

Modeling Magnetic Disk Wind State Transitions in Black Hole X-Ray Binaries

We analyze three prototypical black hole X-ray binaries, 4U 1630–472, GRO J1655–40, and H1743–322, in an effort to systematically understand the intrinsic state transition of the observed accretion disk winds between wind-on and wind-off states by utilizing state-of-the-art Chandra/HETGS archival data from multi-epoch observations. We apply our magnetically driven wind models in the context of magnetohydrodynamic(MHD)calculations to constrain(1)their global density slope(p),(2)their density (n17) at the foot point of the inner most launching radius, and(3)the abundances of heavier elements(AFe,S,Si). Incorporating the MHD winds into xstar photoionization calculations in a self-consistent manner, we create a library of synthetic absorption spectra given the observed X-ray continua. Our analysis clearly indicates a characteristic bimodal transition of multi-ion X-ray winds; i.e., the wind density gradient is found to steepen(fro mp∼1.2–1.4 to∼1.4–1.5)while its density normalization declines as the source transitions from the wind-onto the wind-off state. The model implies that the ionized wind remains physically present even in the wind-off state, despite its apparent absence in the observed spectra. Super solar abundances for heavier elements are also favored. Our global multi-ion wind models, taking into account soft X-ray ions as well as Fe K absorbers, show that the internal wind condition plays an important role in wind transitions besides photoionization changes. Simulated XRISM/Resolve and Athena/X-IFU spectra are presented to demonstrate a high fidelity of the multi-ion wind model for a better understanding of these powerful ionized winds in the coming decades

Keigo Fukumura↗

The Variable Detection of Atmospheric Escape around the Young, Hot Neptune AU Mic b

Photoevaporation is a potential explanation for several features within exoplanet demographics. Atmospheric escape observed in young Neptune-sized exoplanets can provide insight into and characterize which mechanisms drive this evolution and at what times they dominate. AU Mic b is one such exoplanet, slightly larger than Neptune (4.19 R ⊕ ). It closely orbits a 23 Myr pre-main-sequence M dwarf with an orbital period of 8.46 days. We obtained two visits of AU Mic b at Lyα with Hubble Space Telescope (HST)/Space Telescope Imaging Spectrograph. One flare within the first HST visit is characterized and removed from our search for a planetary transit. We present a nondetection in our first visit, followed by the detection of escaping neutral hydrogen ahead of the planet in our second visit. The outflow absorbed ∼30% of the star’s Lyα blue wing 2.5 hr before the planet’s white-light transit. We estimate that the highest-velocity escaping material has a column density of 10 13.96 cm −2 and is moving 61.26 km s −1 away from the host star. AU Mic b’s large high-energy irradiation could photoionize its escaping neutral hydrogen in 44 minutes, rendering it temporarily unobservable. Our time-variable Lyα transit ahead of AU Mic b could also be explained by an intermediate stellar wind strength from AU Mic that shapes the escaping material into a leading tail. Future Lyα observations of this system will confirm and characterize the unique variable nature of its Lyα transit, which, combined with modeling, will tune the importance of stellar wind and photoionization.

Exoplanets↗

Detection Identification and Quantification of Keto-Hydroperoxides in Low-Temperature Oxidation.

Keto-hydroperoxides are reactive partially oxidized intermediates that play a central role in chain-branching reactions during the low-temperature oxidation of hydrocarbons. In this Perspective, we outline how these short lived species can be detected, identified, and quantified using integrated experimental and theoretical approaches. The procedures are based on direct molecular-beam sampling from reactive environments, followed by mass spectrometry with single-photon ionization, identification of fragmentation patterns, and theoretical calculations of ionization thresholds, fragment appearance energies, and photoionization cross sections. Using the oxidation of neo-pentane and tetrahydrofuran as examples, the individual steps of the experimental approaches are described in depth together with a detailed description of the theoretical efforts. For neo-pentane, the experimental data are consistent with the calculated ionization and fragment appearance energies of the keto-hydroperoxide, thus adding confidence to the analysis routines and the employed levels of theory. For tetrahydrofuran, multiple keto-hydroperoxide isomers are possible due to the presence of nonequivalent O 2 addition sites. Despite this additional complexity, the experimental data allow for the identification of two to four keto-hydroperoxides. Mole fraction profiles of the keto-hydroperoxides, which are quantified using calculated photoionization cross sections, are provided together with estimated uncertainties as function of the temperature of the reactive mixture and can serve as validation targets for chemically detailed mechanisms.

Hansen, Nils↗

Shake loss intensities in x-ray photoelectron spectroscopy: Theory, experiment, and atomic composition accuracy for MgO and related compounds

The relative intensities of XPS core levels, scaled by their photoionization cross sections, are regularly used to determine sample atomic composition. Cross sections, however, give the intensity to all possible final states for the core ionizations, not just to the main peak. This includes all intrinsic satellite structure (shake states and, for open shell systems, the different ionic multiplets). In practice, for solids, this is usually experimentally impossible to determine accurately because such a satellite structure sits on the inelastically scattered electron background and cannot be easily separated. Therefore, usually, only the intensity of the main peak is used. This limits the ultimate possible accuracy of XPS composition determination. The purpose of the present paper is to examine the contributions that a theoretical analysis of losses of intensity can make to improve quantitation. For an MgO single crystal, we show that the correct stoichiometry of 1:1 can be recovered using the theoretical analysis of the experimental MgO peak ratio intensities. For materials with a sufficient bandgap for the XPS main peaks to be separated from the scattered background, the intensity of main peaks can often be accurately determined. Thus, if one uses theory to calculate that fraction of the total intensity lost from a main peak into all its satellite structure, the intensity of just main peaks could then be used to more accurately determine relative atom % composition. This work tests this approach using a single crystal MgO (50% Mg, 50% O) standard. Ab initio electronic structure theory of representative MgO clusters is used to determine Hartree–Fock wave functions for the ground state and final ionized states corresponding to the main Mg 2p and O1s XPS peaks of the oxide. The sudden approximation, SA, is used to determine the fractional losses from these main peaks to shake satellites, which is found to be greater for O1s than Mg2p. This results in predicted “apparent composition” for stoichiometric MgO of 55.2% Mg, 44.8% O instead of the true 50% Mg, 50% O. Equivalent theory for CaO results in a predicted apparent Ca value of 53.4%. Experimentally, using Mg2s or 2p intensity ratio to O1s, we find values between 52.2% and 56.0% Mg using two crystals and four different instrument electron pass energies. The average value of the measurements is 54.5% Mg when corrected for the presence of an adventitious carbon overlayer and slight surface hydroxide. Though this agreement with theory may be somewhat fortuitous, given the potential experimental errors, which are fully discussed, it is similar to that in our earlier study on LiF. We also present preliminary experimental data on Mg(OH) 2 and MgSO 4 , which show a similar trend of apparently higher than 50% Mg, but we have no theory values. We are not yet able to experimentally test for validation of the difference between apparent composition for MgO (55.2% Mg) and CaO (53.4% Ca), owing to significant carbonate formation at the surface of the single crystal CaO. Here, an important conclusion is that the theoretical determination of shake losses, obtained with ab initio wavefunctions and the SA, is likely to be a useful way to calibrate the accuracy and reliability of compositions obtained from XPS intensities and merits further study.

47 OTHER INSTRUMENTATION↗

A Simple Method for Improving the Spatial Resolution in Infrared Laser Ablation Mass Spectrometry Imaging

In mass spectrometry imaging of tissues, the size of structures that can be distinguished is determined by the spatial resolution of the imaging technique. Here, the spatial resolution of IR laser ablation is markedly improved by increasing the distance between the laser and the focusing lens. As the distance between the laser and the lens is increased from 1 to 18 m, the ablation spot size decreases from 440 to 44 μm. This way, only the collimated center of the divergent laser beam is directed on the focusing lens, which results in better focusing of the beam. Part of the laser energy is lost at longer distance, but this is compensated by focusing of the radiation to a smaller area on the sample surface. The long distance can also be achieved by a set of mirrors, between which the radiation travels before it is directed to the focusing lens and the sample. This method for improving the spatial resolution can be utilized in mass spectrometry imaging of tissues by techniques that utilize IR laser ablation, such as laser ablation electrospray ionization, laser ablation atmospheric pressure photoionization, and matrix-assisted laser desorption electrospray ionization. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

On the SIMS Ionization Probability of Organic Molecules

The prospect of improved secondary ion yields for secondary ion mass spectrometry (SIMS) experiments drives innovation of new primary ion sources, instrumentation, and post-ionization techniques. The largest factor affecting secondary ion efficiency is believed to be the poor ionization probability (α{sup +}) of sputtered material, a value rarely measured directly, but estimated to be in some cases as low as 10{sup −5}. Our lab has developed a method for the direct determination of α{sup +} in a SIMS experiment using laser post-ionization (LPI) to detect neutral molecular species in the sputtered plume for an organic compound. Here, we apply this method to coronene (C{sub 24}H{sub 12}), a polyaromatic hydrocarbon that exhibits strong molecular signal during gas-phase photoionization. A two-dimensional spatial distribution of sputtered neutral molecules is measured and presented. It is shown that the ionization probability of molecular coronene desorbed from a clean film under bombardment with 40 keV C{sub 60} cluster projectiles is of the order of 10{sup −3}, with some remaining uncertainty arising from laser-induced fragmentation and possible differences in the emission velocity distributions of neutral and ionized molecules. In general, this work establishes a method to estimate the ionization efficiency of molecular species sputtered during a single bombardment event. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Design and Evaluation of a Gas Chromatograph-Atmospheric Pressure Chemical Ionization Interface for an Exactive Orbitrap Mass Spectrometer

Various separation and mass spectrometric (MS) techniques have furthered our ability to study complex mixtures, and the desire to measure every analyte in a system is of continual interest. For many complex mixtures, such as the total molecular content of a cell, it is becoming apparent that no one single separation technique or analysis is likely to achieve this goal. Therefore, having a variety of tools to measure the complexity of these mixtures is prudent. Orbitrap MSs are broadly used in systems biology studies due to their unique performance characteristics. However, GC-Orbitraps have only recently become available, and instruments that can use gas chromatography (GC) cannot use liquid chromatography (LC) and vice versa. This limits small molecule analyses, such as those that would be employed for metabolomics, lipidomics, or toxicological studies. Thus, a simple, temporary interface was designed for a GC and Thermo Scientific™ Ion Max housing unit. This interface enables either GC or LC separation to be used on the same MS, an Exactive™ Plus Orbitrap, and utilizes an atmospheric pressure chemical ionization (APCI) source. The GC-APCI interface was tested against a commercially available atmospheric pressure photoionization (APPI) interface for three types of analytes that span the breadth of typical GC analyses: fatty acid methyl esters (FAMEs), polyaromatic hydrocarbons (PAHs), and saturated hydrocarbons. The GC-APCI-Orbitrap had similar or improved performance to the APPI and other reported methods in that it had a lower limit of quantitation, better signal to noise, and lower tendency to fragment analytes. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Radiative recombination data for tungsten ions: II. W{sup 47+}–W{sup 71+}

New radiative recombination and photoionization cross sections, radiative recombination rate coefficients, and radiated power loss rate coefficients are presented for 23 tungsten impurity ions in plasmas. We consider ions from W{sup 47+} to W{sup 71+} that are of importance to fusion studies for ITER and for experiments using electron beam ion traps. The calculations are fully relativistic and all significant multipoles of the radiative field are taken into account. The Dirac–Fock method is used to compute the electron wavefunctions. Radiative recombination rates and radiated power loss rates are found using the relativistic Maxwell–Jüttner distribution of the continuum electron velocity. The total radiative recombination cross sections are given in the electron energy range from 1 eV to ∼80keV. Partial cross sections for ground and excited states are approximated by an analytical expression involving five fit parameters. Radiative recombination rates and radiated power loss rates are calculated in the temperature range from 10{sup 4}K to 10{sup 9}K. The total radiative recombination rates are approximated by another analytical expression with four fit parameters.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Air quality impacts from the development of unconventional oil and gas well pads: Air toxics and other volatile organic compounds

Unconventional oil and natural gas development (UOGD) has expanded rapidly across the United States in recent decades and raised concerns about associated air quality impacts. While significant effort has been made to quantify methane emissions, relatively few observations have been made of Volatile Organic Compounds (VOCs), especially during drilling and completion of new wells. Extensive air monitoring during development of several large, multi-well pads in Broomfield, Colorado, in the Denver-Julesburg Basin, provides a novel opportunity to examine changes in local air toxics and other VOC concentrations during well drilling and completions and production. These operations offer an especially useful case to study as several management practices were implemented to reduce emissions (e.g., electrified, grid-powered drill rigs and closed loop fluid handling systems to reduce truck traffic and limit fluid handling on the pad). With simultaneous measurements of methane and 50 VOCs from October 2018 to December 2022 at as many as 19 sites near well pads, in adjacent neighborhoods, and at a more distant reference location, we identify impacts from each phase of well development and production. Use of weekly, time-integrated canisters, a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous photoionization detectors (PID) to trigger canister collection upon detection of VOC-rich plumes, and an instrumented vehicle, provided a powerful suite of measurements to characterize both transient plumes and longer-term changes in air quality. Prior to the start of well development, VOC gradients were small across Broomfield. Once drilling commenced, concentrations of oil and gas (O&G) related VOCs, including alkanes and aromatics, increased around active well pads. Concentration increases were clearly apparent during certain operations, including drilling, coil tubing/millout operations, and production tubing installation. Emissions of C 8 –C 10 n-alkanes during drilling operations highlighted the importance of VOC emissions from synthetic drilling mud chosen to reduce odor impacts. More than 90 samples were collected of transient plumes. Using composition measurements, meteorological data, and information about well pad activities, these plumes were connected with specific UOGD operations including drilling, flowback, and production equipment maintenance. The chemical signatures of these plumes differed by operation type (e.g., C 8 –C 10 n-alkanes constituted a larger fraction of measured VOCs in drilling-related plumes). Concentrations of individual, oil and gas-related VOCs in these plumes were often several orders of magnitude higher than in background air, with maximum ethane and benzene concentrations of 79,600 and 819 ppbv, respectively. Because these plumes typically impact a monitoring site for just several minutes, they are easily missed by slower-responding instruments. Study measurements highlight future emission mitigation opportunities during UOGD operations, including better control of emissions from shakers that separate drill cuttings from drilling mud, production separator maintenance operations, and periodic emptying of sand cans during flowback operations.

54 ENVIRONMENTAL SCIENCES↗

Additional chain-branching pathways in the low-temperature oxidation of branched alkanes

Chain-branching reactions represent a general motif in chemistry, encountered in atmospheric chemistry, combustion, polymerization, and photochemistry; the nature and amount of radicals generated by chain-branching are decisive for the reaction progress, its energy signature, and the time towards its completion. In this study, experimental evidence for two new types of chain-branching reactions is presented, based upon detection of highly oxidized multifunctional molecules (HOM) formed during the gas-phase low-temperature oxidation of a branched alkane under conditions relevant to combustion. The oxidation of 2,5-dimethylhexane (DMH) in a jet-stirred reactor (JSR) was studied using synchrotron vacuum ultra-violet photoionization molecular beam mass spectrometry (SVUV-PI-MBMS). Specifically, species with four and five oxygen atoms were probed, having molecular formulas of C 8 H 14 O 4 (e.g., diketo-hydroperoxide/keto-hydroperoxy cyclic ether) and C 8 H 16 O 5 (e.g., keto-dihydroperoxide/dihydroperoxy cyclic ether), respectively. The formation of C 8 H 16 O 5 species involves alternative isomerization of OOQOOH radicals via intramolecular H-atom migration, followed by third O 2 addition, intramolecular isomerization, and OH release; C 8 H 14 O 4 species are proposed to result from subsequent reactions of C 8 H 16 O 5 species. The mechanistic pathways involving these species are related to those proposed as a source of low-volatility highly oxygenated species in Earth's troposphere. At the higher temperatures relevant to auto-ignition, they can result in a net increase of hydroxyl radical production, so these are additional radical chain-branching pathways for ignition. Furthermore, the results presented herein extend the conceptual basis of reaction mechanisms used to predict the reaction behavior of ignition, and have implications on atmospheric gas-phase chemistry and the oxidative stability of organic substances.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

n-Heptane cool flame chemistry: Unraveling intermediate species measured in a stirred reactor and motored engine

This paper identifies classes of cool flame intermediates from n-heptane low-temperature oxidation in a jet-stirred reactor (JSR) and a motored cooperative fuel research (CFR) engine. The sampled species from the JSR oxidation of a mixture of n-heptane/O 2 /Ar (0.01/0.11/0.88) were analyzed using a synchrotron vacuum ultraviolet radiation photoionization (SVUV-PI) time-of-flight molecular-beam mass spectrometer (MBMS) and an atmospheric pressure chemical ionization (APCI) Orbitrap mass spectrometer (OTMS). The OTMS was also used to analyze the sampled species from a CFR engine exhaust. Approximately 70 intermediates were detected by the SVUV-PI-MBMS, and their assigned molecular formulae are in good agreement with those detected by the APCI-OTMS, which has ultra-high mass resolving power and provides an accurate elemental C/H/O composition of the intermediate species. Furthermore, the results show that the species formed during the partial oxidation of n-heptane in the CFR engine are very similar to those produced in an ideal reactor, i.e., a JSR. The products can be classified by species with molecular formulae of C 7 H 14 O x (x = 0–5), C 7 H 12 O x (x = 0–4), C 7 H 10 O x (x = 0–4), C n H 2n (n = 2–6), C n H 2n-2 (n = 4–6), C n H 2n+2 O (n = 1–4), C n H 2n O (n = 1–6), C n H 2n-2 O (n = 2–6), C n H 2n-4 O (n = 4–6), C n H 2n+2 O 2 (n = 0–4, 7), C n H 2n O 2 (n = 1–6), C n H 2n-2 O 2 (n = 2–6), C n H 2n-4 O 2 (n = 4–6), and C n H 2n O 3 (n = 3–6). The identified intermediate species include alkenes, dienes, aldehyde/keto compounds, olefinic aldehyde/keto compounds, diones, cyclic ethers, peroxides, acids, and alcohols/ethers. Reaction pathways forming these intermediates are proposed and discussed herein. Finally, these experimental results are important in the development of more accurate kinetic models for n-heptane and longer-chain alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Moving your laboratories to the field – Advantages and limitations of the use of field portable instruments in environmental sample analysis

The recent rapid progress in technology of field portable instruments has increased their applications in environmental sample analysis. These instruments offer a possibility of cost-effective, non-destructive, real-time, direct, on-site measurements of a wide range of both inorganic and organic analytes in gaseous, liquid and solid samples. Some of them do not require the use of reagents and do not produce any analytical waste. All these features contribute to the greenness of field portable techniques. Several stationary analytical instruments have their portable versions. The most popular ones include: gas chromatographs with different detectors (mass spectrometer (MS), flame ionization detector, photoionization detector), ultraviolet–visible and near-infrared spectrophotometers, X-ray fluorescence spectrometers, ion mobility spectrometers, electronic noses and electronic tongues. The use of portable instruments in environmental sample analysis gives a possibility of on-site screening and a subsequent selection of samples for routine laboratory analyses. They are also very useful in situations that require an emergency response and for process monitoring applications. However, quantification of results is still problematic in many cases. The other disadvantages include: higher detection limits and lower sensitivity than these obtained in laboratory conditions, a strong influence of environmental factors on the instrument performance and a high possibility of sample contamination in the field. This paper reviews recent applications of field portable instruments in environmental sample analysis and discusses their analytical capabilities. - Highlights: • Field portable instruments are widely used in environmental sample analysis. • Field portable instruments are indispensable for analysis in emergency response. • Miniaturization of field portable instruments reduces resource consumption. • In situ analysis is in agreement with green analytical chemistry principles. • Performance requirements in field analysis stimulate technological progress.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Long duration X-ray drive hydrodynamics experiments relevant for laboratory astrophysics

The advent of high-power lasers facilities such as the National Ignition Facility (NIF), and the Laser Megajoule (LMJ) in the near future, opens a new era in the field of High Energy Density Laboratory Astrophysics. These versatile laser facilities will provide unique platforms to study the rich physics of nonlinear and turbulent mixing flows. The extended laser pulse duration could be harnessed to accelerate targets over much larger distances and longer time periods than previously achieved. Here, we report on the first results acquired on NIF with the ablative Rayleigh–Taylor Instability (RTI) platform. A 20-ns X-ray drive is tailored to accelerate planar modulated samples into the highly-nonlinear bubble merger regime. Based on the analogy between flames front and ablation front, highly nonlinear RTI measurements at ablation front can provide important insights into the initial deflagration stage of thermonuclear supernova of Type Ia. We also report on an innovative concept used to create even longer drive on multi-beam laser facilities. The multi-barrel hohlraum (Gattling Gun) approach consists, here, of three adjacent cavities, driven in succession in time. This novel concept has been validated on the Omega EP laser system. The three cavities were irradiated with three 6–10 ns pulse UV beams and a 30 ns, 90 eV X-ray radiation drive was measured with the time-resolved X-ray spectrometer μDMX. This concept is promising to investigate the pillar structures in the Eagle Nebula or for photoionization studies which require a steady light source of sufficient duration to recreate relevant physics.

Molecular clouds↗

Thermostability and photostability of Sr{sub 3}SiO{sub 5}:Eu{sup 2+} phosphors for white LED applications

Sr{sub 3}SiO{sub 5}:Eu{sup 2+} phosphors were synthesized by solid-state reactions, and their photoluminescence (PL) stability under the impact of heat or light was studied. The thermal degradation in air was observed for the Sr{sub 3}SiO{sub 5}:Eu{sup 2+} phosphor, furthermore, this drop in emission intensity could be accelerated by simultaneously illuminating the phosphor with a high-power blue LED during the heating process. This enhanced thermal degradation phenomenon in the blue light can be ascribed to the photo-assisted thermal oxidation of Eu{sup 2+} ions. A reversible decrease in emission intensity at room temperature was observed on illuminating the Sr{sub 3}SiO{sub 5}:Eu{sup 2+} phosphor alone by the blue light, which could be related to trapping centers in the phosphor. The existence of traps is also responsible for the anomalous increase of emission intensity with increasing temperature from 30 to 100 °C. Considering the influences of Ba{sup 2+} doping on temperature-dependent PL properties of the Sr{sub 3}SiO{sub 5}:Eu{sup 2+} phosphor, the thermal quenching origin may be ascribed to the thermally assisted photoionization process. - Graphical abstract: The photo-induced reversible decrease in emission intensity and the anomalous emission enhancement with increasing temperature are related to trapping centers in the phosphor. - Highlights: • The photo-assisted thermal degradation was observed for the Sr{sub 3}SiO{sub 5}:Eu{sup 2+} phosphor. • The phosphor showed a reversible intensity decrease under the blue light irradiation. • An anomalous emission enhancement with increasing temperature was found. • Ba{sup 2+} substitution could suppress the thermal quenching of Sr{sub 3}SiO{sub 5}:Eu{sup 2+}. • Mechanisms for photostability and thermostability were discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Luminescence properties of Eu{sup 2+} doped SrB{sub 4}O{sub 7} phosphor for radiation dosimetry

Highlights: • Report TL/OSL properties of SrB{sub 4}O{sub 7}:Eu{sup 2+} under beta irradiations. • OSL Sensitivity was about 33% than that of commercially available α-Al{sub 2}O{sub 3.} • TL glow peaks was appear at 305° C and TL sensitivity about 200 times higher than TLD-500. • OSL decay pattern was faster than α- Al{sub 2}O{sub 3}:C and dose response was linear nature. - Abstract: In this report, we presented the TL/OSL properties of Eu doped SrB{sub 4}O{sub 7} phosphor under β-irradiation. This phosphor was synthesized by using solid state method. The phosphor shows OSL sensitivity about 33% than that of commercially available α-Al{sub 2}O{sub 3}: C phosphor. CW-OSL curve possess two components having photoionization cross-sections 0.707 × 10{sup −17} and 18.58 × 10{sup −17} cm{sup 2} respectively and TL sensitivity about 200 times higher than TLD-500. The kinetic parameters such as activation energy, frequency factor and order of kinetics of TL curve were calculated by using peak shape method. In TL/OSL mode dose-response was almost linear in the range of measurements. The MDD was found to be 1.26 mGy with 3σ of background. Also reusability studies showed the phosphor can be reused for 10 cycles with 1% change in the OSL output. The PL spectra of SrB{sub 4}O{sub 7} showed emission in NUV region when excited with 318 nm under UV source.

36 MATERIALS SCIENCE↗

TL/OSL properties of beta irradiated Al2O3:Tm3+ phosphor synthesized by microwave combustion method

Highlights: • TL emission spectra of γ – rayed Al{sub 2}O{sub 3}:Tm{sup 3+} shows Tm{sup 3+} characteristic transitions. • Doping of Tm{sup 3+} ions causes enhancement of TL/OSL. • TL/OSL kinetic parameters are analyzed by CGCD method. • TL mechanism of γ/β – rayed Al{sub 2}O{sub 3}:Tm{sup 3+} was proposed. • TL/OSL dosimetric properties of Al{sub 2}O{sub 3}:Tm{sup 3+} suggests that the material is appropriate for medical dosimetry. - Abstract: This work discusses synthesis of stable α-phase of Al{sub 2}O{sub 3}:Tm{sup 3+} by combustion method using temperature controlled microwave oven. The crystalline phase was analyzed by X-ray diffraction (XRD) technique and average crystallite size was found to be 147 nm. Observations using scanning electron microscope (SEM) image suggest formation of agglomerated particles and energy dispersive x-ray spectroscopy (EDS) confirmed the incorporation of Tm{sup 3+} in Al{sub 2}O{sub 3}. Thermoluminescence emission (TLE) spectrum of γ – irradiated Al{sub 2}O{sub 3}:Tm{sup 3+} shows characteristic emissions of Tm{sup 3+}, Cr{sup 3+} and Mn{sup 4+}. TL glow curves of γ – irradiated Al{sub 2}O{sub 3}:Tm{sup 3+} exhibit a prominent peak at 453 K along with a shoulder at 496 K. The glow curves of β – irradiated Al{sub 2}O{sub 3}:Tm{sup 3+} were studied in different emission regions using U340 + BG39 (UV band pass), CS759 + BG39 (Blue band pass) and BG39 (Visible band pass) optical glass filters. A prominent peak was observed at 471 K in for all mentioned emission regions and an additional shoulder was observed at 511 K with CS759 + BG39 and BG39 filters. TL glow curve of β – irradiated Al{sub 2}O{sub 3}:Tm{sup 3+} using only BG39 filter had more counts than CS759 + BG39 and U340 + BG39 filters. Further, the effect of Tm{sup 3+} impurity on TL response was studied. TL kinetic parameters were estimated by using computerized glow curve deconvolution (CGCD) technique. The activation energy and frequency factor of prominent peak (471 K) were found to be 1.31 eV and 3.50 × 10{sup 13} s{sup −1} respectively. Optically stimulated luminescence (OSL) characteristics of β – irradiated Al{sub 2}O{sub 3}:Tm{sup 3+} were studied using U340 + BG39 and CS759 + BG39 filters. Highest OSL intensity was observed in UV. OSL curves were deconvoluted by general order decay equation. Life time and photoionization cross section of the traps responsible for OSL were found to be 5.30 s and 3.98 × 10{sup −18} cm{sup 2} respectively. The process of ionization of electron from Tm{sup 3+}, electron trap in host lattice and its recombination mechanism is proposed. Phosphorescence decay of beta irradiated sample was also studied. The lifetime of phosphorescence decay was found to be 140 s for the prominent peak and TL intensity decays 25% after the phosphorescence. TL/OSL dosimetric properties viz. linearity with dose, reusability and minimum detectable dose of the phosphor were characterized for medical dosimetry application.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

New insights into the low-temperature oxidation of 2-methylhexane

The low-temperature oxidation of a stoichiometric 2-methylhexane/O 2 /Ar mixture was examined in a jet-stirred reactor coupled with synchrotron vacuum UV photoionization molecular-beam MS. The initial gas mixture was composed of 2% 2-methyhexane, 22% O 2 and 76% Ar and the pressure of the reactor was kept at 780 Torr. Low-temperature oxidation intermediates with two to five oxygen atoms were observed. The detection of C 7 H 14 O 5 and C 7 H 12 O 4 species suggests that a third O 2 addition process occurs in 2-methylhexane low-temperature oxidation. A detailed kinetic model was developed that describes the third O 2 addition and subsequent reactions leading to C 7 H 14 O 5 (keto-dihydroperoxide and dihydroperoxy cyclic ether) and C 7 H 12 O 4 (diketo-hydroperoxide and keto-hydroperoxy cyclic ether) species. The kinetics of the third O 2 addition reactions are discussed and model calculations were performed that reveal that third O 2 addition reactions promote 2-methylhexane auto-ignition at low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental Evidence of Dioxole Unimolecular Decay Pathway for Isoprene-Derived Criegee Intermediates

Ozonolysis of isoprene, one of the most abundant volatile organic compounds emitted into the Earth’s atmosphere, generates two four-carbon unsaturated Criegee intermediates, methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide). The extended conjugation between the vinyl substituent and carbonyl oxide groups of these Criegee intermediates facilitates rapid electrocyclic ring closures that form 5-membered cyclic peroxides, known as dioxoles. This research discusses the first experimental evidence of this novel decay pathway, which is predicted to be the dominant atmospheric sink for specific conformational forms of MVK-oxide (anti) and MACR-oxide (syn) with the vinyl substituent adjacent to the terminal O atom. The resulting dioxoles are predicted to undergo rapid unimolecular decay to oxygenated hydrocarbon radical products, including acetyl, vinoxy, formyl, and 2-methyl-vinoxy radicals. In the presence of O 2 , these radicals rapidly react to form peroxy radicals (ROO), which quickly decay via carbon-centered radical intermediates (QOOH) to stable carbonyl products that are identified in this work. The carbonyl products are detected under thermal conditions (298 K, 10 torr He) using multiplexed photoionization mass spectrometry (MPIMS). The main products (and associated relative abundances) originating from unimolecular decay of anti-MVK-oxide and subsequent reaction with O 2 are formaldehyde (88 ± 5%), ketene (9 ± 1%) and glyoxal (3 ± 1%). Those identified from the unimolecular decay of syn-MACR-oxide and subsequent reaction of O 2 are acetaldehyde (37 ± 7%), vinyl alcohol (9 ± 1%), methylketene (2 ± 1%), and acrolein (52 ± 5%). In addition to the stable carbonyl products, the secondary peroxy chemistry also generates OH or HO 2 radical co-products.

09 BIOMASS FUELS↗