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At least 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Identification of analog states in the T=1/2 A=27 mirror system from low excitation energies to the region of hydrogen burning in the {sup 26}Al{sup g,m}(p,{gamma}){sup 27}Si reactions

The reactions {sup 26}Al{sup g}(p, {gamma}){sup 27}Si and {sup 26}Al{sup m}(p, {gamma}){sup 27}Si are important for influencing the galactic abundance of the cosmic {gamma}-ray emitter {sup 26}Al{sup g} and for the excess abundance of {sup 26}Mg found in presolar grains, respectively. Precise excitation energies and spin assignments of states from the ground state to the region of astrophysical interest in {sup 27}Si, including the identification and pairing of key astrophysical resonances with analog states in the mirror nucleus {sup 27}Al, are reported using {gamma} rays observed in the {sup 12}C + {sup 16}O fusion reaction. The detailed evolution of Coulomb energy differences between the states in {sup 27}Si and {sup 27}Al is explored, including the region above the astrophysical reaction thresholds.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2014

TU-C-BRE-09: Performance Comparisons of Patient Specific IMRT QA Methodologies Using ROC Analysis

Purpose: To evaluate the ability of a selection of patient-specific QA methods to accurately classify IMRT plans as acceptable or unacceptable based on a multiple ion chamber (MIC) phantom. Methods: Twenty-four IMRT plans were selected (20 previously failed the institutional QA), and were measured on a MIC phantom to assess their dosimetric acceptability. These same plans were then measured using film (Kodak EDR2) and ion chamber (Wellhofer cc04), ArcCheck (Sun Nuclear), and MapCheck (Sun Nuclear) (delivered AP field-by-field, AP composite, and with original gantry angles). All gamma analyses were performed at 2%/2mm, 3%/3mm, and 5%/3mm. By using the MIC results as a gold standard, the sensitivity and specificity were calculated across a range of cut-off thresholds (% pixels passing for gamma analysis, and % dose difference for ion chamber), and were used to form ROC curves. Area under the curve (AUC) was used as a metric to quantify the performance of the various QA methods. Results: Grouping device’s AUC’s revealed two statistically significant different groups: ion chamber (AUC of 0.94), AP composite MapCheck (AUC of 0.85), ArcCheck (AUC of 0.84), and film (AUC of 0.82) were in the better performing group, while original gantry angles and AP field-by-field MapCheck (AUC of 0.65 and 0.66, respectively) matched less well with the gold standard results. Optimal cut-offs were also assessed using the ROC curves. We found that while often 90% of pixels passing is used as a criteria, the differing sensitivities of QA methods can lead to device and methodology-based optimal cutoff thresholds. Conclusion: While many methods exist to perform the same task of patient-specific IMRT QA, they utilize different strategies. This work has shown that there are inconsistencies in these methodologies in terms of their sensitivity and specificity to dosimetric acceptability. This work was supported by Public Health Service grants CA010953, CA081647, and CA21661 awarded by the National Cancer Institute, United States Department of Health and Human Services.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2012

Investigation of the spatial resolution of an online dose verification device

Purpose: The aim of this work is to characterize a new online dose verification device, COMPASS transmission detector array (IBA Dosimetry, Schwarzenbruck, Germany). The array is composed of 1600 cylindrical ionization chambers of 3.8 mm diameter, separated by 6.5 mm center-to-center spacing, in a 40 x 40 arrangement. Methods: The line spread function (LSF) of a single ion chamber in the detector was measured with a narrow slit collimator for a 6 MV photon beam. The 0.25 x 10 mm{sup 2} slit was formed by two machined lead blocks. The LSF was obtained by laterally translating the detector in 0.25 mm steps underneath the slit over a range of 24 mm and taking a measurement at each step. This measurement was validated with Monte Carlo simulation using BEAMnrc and DOSXYZnrc. The presampling modulation transfer function (MTF), the Fourier transform of the line spread function, was determined and compared to calculated (Monte Carlo and analytical) MTFs. Two head-and-neck intensity modulated radiation therapy (IMRT) fields were measured using the device and were used to validate the LSF measurement. These fields were simulated with the BEAMnrc Monte Carlo model, and the Monte Carlo generated incident fluence was convolved with the 2D detector response function (derived from the measured LSF) to obtain calculated dose. The measured and calculated dose distributions were then quantitatively compared using {chi}-comparison criteria of 3% dose difference and 3 mm distance-to-agreement for in-field points (defined as those above the 10% maximum dose threshold). Results: The full width at half-maximum (FWHM) of the measured detector response for a single chamber is 4.3 mm, which is comparable to the chamber diameter of 3.8 mm. The pre-sampling MTF was calculated, and the resolution of one chamber was estimated as 0.25 lp/mm from the first zero crossing. For both examined IMRT fields, the {chi}-comparison between measured and calculated data show good agreement with 95.1% and 96.3% of in-field points below {chi} of 1.0 for fields 1 and 2, respectively (with an average {chi} of 0.29 for IMRT field 1 and 0.24 for IMRT field 2). Conclusions: The LSF for a new novel online detector has been measured at 6 MV using a narrow slit technique, and this measurement has been validated by Monte Carlo simulation. The detector response function derived from line spread function has been applied to recover measured IMRT fields. The results have shown that the device measures IMRT fields accurately within acceptable tolerance.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2017

Mitigation of hot electrons from laser-plasma instabilities in high-Z, highly ionized plasmas

Intense lasers interacting with under-dense plasma can drive laser-plasma instabilities (LPIs) that generate largeamplitude electron plasma waves (EPWs). Suprathermal or “hot” electrons produced in the EPWs are detrimental to inertial confinement fusion (ICF), by reducing capsule implosion efficiency through preheat, and also present an unwanted source of background on x-ray diagnostics. Mitigation of hot electrons was demonstrated in the past by altering plasma conditions near the quarter-critical density, n c /4, with the interpretation of reduced growth of the twoplasmon decay (TPD) instability. Here, we present measurements of hot electrons generated in laser-irradiated planar foils of material ranging from low- to high-Z, where the fraction of laser energy converted to hot electrons, fhot was reduced by a factor of 10 3 going from CH to Au. This correlates with steepening density gradient length-scales that were also measured. Radiation hydrodynamic simulations produced electron density profiles in reasonable agreement with our measurements. According to the simulations, both multi-beam TPD and stimulated Raman scattering were predicted to be above threshold with linear threshold parameters that decreased with increasing Z due to steepening length-scales, as well as enhanced laser absorption and increased EPW collisional and Landau damping.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Coherence and quasistable states in a strong infrared field

We study the quasistability of UV-pulse-train-excited H atoms in a strong infrared (IR) laser as a function of the phase delay of the UV pulse train relative to the IR laser. The UV pulse train contains two frequency components. When the two components have frequencies separated by two IR photons, the population of surviving electrons is modulated by up to ten percent. When electrons are excited to right above or below the threshold, the survival probabilities have inverted phase delay dependence, which can be explained classically. When the two frequencies are one IR photon apart, the angular symmetry of the quasistable electrons is broken, and the asymmetry is also controlled by the phase delay. Here, the asymmetrical distribution can be observed while the IR is on and smoothly evolves to a nonzero asymmetry that only weakly depends on the duration of the IR field.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2016

Photoionization and photofragmentation of the C 60 + molecular ion

Cross-section measurements are reported for single and double photoionization of C$+\atop{60}$ ions in the photon energy range 18-150 eV accompanied by the loss of zero to seven pairs of carbon atoms, as well as for fragmentation without ionization resulting in loss of two to eight pairs of C atoms in the photon energy range 18-65 eV. Absolute measurements were performed by merging a beam of C$+\atop{60}$ molecular ions with a beam of monochromatized synchrotron radiation. Product channels involving dissociation yielding smaller fullerene fragment ions account for nearly half of the total measured oscillator strength in this energy range. The sum of cross sections for the measured product channels is compared to a published calculation of the total photoabsorption cross section of neutral C 60 based on time-dependent density-functional theory. Lastly, this comparison and an accounting of oscillator strengths indicate that with the exception of C$+\atop{58}$, the most important product channels resulting from photoabsorption were accounted for in the experiment. Threshold energies for the successive removal of carbon atom pairs accompanying photoionization are also determined from the measurements.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

Metallicity inhomogeneities in local star-forming galaxies as a sign of recent metal-poor gas accretion

We measure the oxygen metallicity of the ionized gas along the major axis of seven dwarf star-forming galaxies. Two of them, SDSSJ1647+21 and SDSSJ2238+14, show ≅0.5 dex metallicity decrements in inner regions with enhanced star formation activity. This behavior is similar to the metallicity drop observed in a number of local tadpole galaxies by Sánchez Almeida et al., and was interpreted as showing early stages of assembling in disk galaxies, with the star formation sustained by external metal-poor gas accretion. The agreement with tadpoles has several implications. (1) It proves that galaxies other than the local tadpoles present the same unusual metallicity pattern. (2) Our metallicity inhomogeneities were inferred using the direct method, thus discarding systematic errors usually attributed to other methods. (3) Taken together with the tadpole data, our findings suggest a threshold around one-tenth the solar value for the metallicity drops to show up. Although galaxies with clear metallicity drops are rare, the physical mechanism responsible for them may sustain a significant part of the star formation activity in the local universe. We argue that the star formation dependence of the mass-metallicity relationship, as well as other general properties followed by most local disk galaxies, is naturally interpreted as side effects of pristine gas infall. Alternatives to the metal-poor gas accretion are examined as well.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

SU-E-T-250: Determining VMAT Machine Limitations of An Elekta Linear Accelerator with Agility MLC for Accurate Modeling in RayStation and Robust Delivery

Purpose: To implement VMAT in RayStation with the Elekta Synergy linac with the new Agility MLC, and to utilize the same vendor softwares to determine the optimum Elekta VMAT machine parameters in RayStation for accurate modeling and robust delivery. Methods: iCOMCat is utilized to create various beam patterns with user defined dose rate, gantry, MLC and jaw speed for each control point. The accuracy and stability of the output and beam profile are qualified for each isolated functional component of VMAT delivery using ion chamber and Profiler2 with isocentric mounting fixture. Service graphing on linac console is used to verify the mechanical motion accuracy. The determined optimum Elekta VMAT machine parameters were configured in RayStation v4.5.1. To evaluate the system overall performance, TG-119 test cases and nine retrospective VMAT patients were planned on RayStation, and validated using both ArcCHECK (with plug and ion chamber) and MapCHECK2. Results: Machine output and profile varies <0.3% when only variable is dose rate (35MU/min-600MU/min). <0.9% output and <0.3% profile variation are observed with additional gantry motion (0.53deg/s–5.8deg/s both directions). The output and profile variation are still <1% with additional slow leaf motion (<1.5cm/s both direction). However, the profile becomes less symmetric, and >1.5% output and 7% profile deviation is seen with >2.5cm/s leaf motion. All clinical cases achieved comparable plan quality as treated IMRT plans. The gamma passing rate is 99.5±0.5% on ArcCheck (<3% iso center dose deviation) and 99.1±0.8% on MapCheck2 using 3%/3mm gamma (10% lower threshold). Mechanical motion accuracy in all VMAT deliveries is <1°/1mm. Conclusion: Accurate RayStation modeling and robust VMAT delivery is achievable on Elekta Agility for <2.5cm/s leaf motion and full range of dose rate and gantry speed determined by the same vendor softwares. Our TG-119 and patient results have provided us with the confidence to use VMAT clinically.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

Investigation on properties of ultrafast switching in a bulk gallium arsenide avalanche semiconductor switch

Properties of ultrafast switching in a bulk gallium arsenide (GaAs) avalanche semiconductor switch based on semi-insulating wafer, triggered by an optical pulse, were analyzed using physics-based numerical simulations. It has been demonstrated that when a voltage with amplitude of 5.2 kV is applied, after an exciting optical pulse with energy of 1 μJ arrival, the structure with thickness of 650 μm reaches a high conductivity state within 110 ps. Carriers are created due to photons absorption, and electrons and holes drift to anode and cathode terminals, respectively. Static ionizing domains appear both at anode and cathode terminals, and create impact-generated carriers which contribute to the formation of electron-hole plasma along entire channel. When the electric field in plasma region increases above the critical value (∼4 kV/cm) at which the electrons drift velocity peaks, a domain comes into being. An increase in carrier concentration due to avalanche multiplication in the domains reduces the domain width and results in the formation of an additional domain as soon as the field outside the domains increases above ∼4 kV/cm. The formation and evolution of multiple powerfully avalanching domains observed in the simulations are the physical reasons of ultrafast switching. The switch exhibits delayed breakdown with the characteristics affected by biased electric field, current density, and optical pulse energy. The dependence of threshold energy of the exciting optical pulse on the biased electric field is discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Real-time breath analysis towards a healthy human breath profile

Abstract The direct analysis of molecules contained within human breath has had significant implications for clinical and diagnostic applications in recent decades. However, attempts to compare one study to another or to reproduce previous work are hampered by: variability between sampling methodologies, human phenotypic variability, complex interactions between compounds within breath, and confounding signals from comorbidities. Towards this end, we have endeavored to create an averaged healthy human ‘profile’ against which follow-on studies might be compared. Through the use of direct secondary electrospray ionization combined with a high-resolution mass spectrometry and in-house bioinformatics pipeline, we seek to curate an average healthy human profile for breath and use this model to distinguish differences inter- and intra-day for human volunteers. Breath samples were significantly different in PERMANOVA analysis and ANOSIM analysis based on Time of Day, Participant ID, Date of Sample, Sex of Participant, and Age of Participant ( p < 0.001). Optimal binning analysis identify strong associations between specific features and variables. These include 227 breath features identified as unique identifiers for 28 of the 31 participants. Four signals were identified to be strongly associated with female participants and one with male participants. A total of 37 signals were identified to be strongly associated with the time-of-day samples were taken. Threshold indicator taxa analysis indicated a shift in significant breath features across the age gradient of participants with peak disruption of breath metabolites occurring at around age 32. Forty-eight features were identified after filtering from which a healthy human breath profile for all participants was created.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

SU-E-T-67: A Quality Assurance Procedure for VMAT Delivery Technique with Multiple Verification Metric Using TG-119 Protocol

Purpose: A successful VMAT plan delivery includes precise modulations of dose rate, gantry rotational and multi-leaf collimator shapes. The purpose of this research is to construct routine QA protocol which focuses on VMAT delivery technique and to obtain a baseline including dose error, fluence distribution and mechanical accuracy during VMAT. Methods: The mock prostate, head and neck (HN) cases supplied from AAPM were used in this study. A VMAT plans were generated in Monaco TPS according to TG-119 protocol. Plans were created using 6 MV and 10 MV photon beams for each case. The phantom based measurement, fluence measurement and log files analysis were performed. The dose measurement was performed using 0.6 cc ion chamber, which located at isocenter. The fluence distribution were acquired using the MapCHECK2 mounted in the MapPHAN. The trajectory log files recorded inner 20 leaf pairs and gantry angle positions at every 0.25 sec interval were exported to in-house software developed by MATLAB and determined those RMS values. Results: The dose difference is expressed as a ratio of the difference between measured and planned doses. The dose difference for 6 MV was 0.91%, for 10 MV was 0.67%. In turn, the fluence distribution using gamma criteria of 2%/2 mm with a 50% minimum dose threshold for 6 MV was 98.8%, for 10 MV was 97.5%, respectively. The RMS values of MLC for 6 MV and 10 MV were 0.32 mm and 0.37 mm, of gantry were 0.33 degree and 0.31 degree. Conclusion: In this study, QA protocol to assess VMAT delivery accuracy is constructed and results acquired in this study are used as a baseline of VMAT delivery performance verification.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

First operation of a multi-channel Q-Pix prototype: measuring transverse electron diffusion in a gas time projection chamber

We report measurements of the transverse diffusion of electrons in P-10 gas (90% Ar, 10% CH 4 ) in a laboratory-scale time projection chamber (TPC) utilizing a novel pixelated signal capture and digitization technique known as Q-Pix. The Q-Pix method incorporates a precision switched integrating transimpedance amplifier whose output is compared to a threshold voltage. Upon reaching the threshold, a comparator sends a 'reset' signal, initiating a discharge of the integrating capacitor. The time difference between successive resets is inversely proportional to the average current at the pixel in that time interval, and the number of resets is directly proportional to the total collected charge. We developed a 16-channel Q-Pix prototype fabricated from commercial off-the-shelf components and coupled them to 16 concentric annular anode electrodes to measure the spatial extent of the electron swarm that reaches the anode after drifting through the uniform field of the TPC. The swarm is produced at a gold photocathode using pulsed UV light. The measured transverse diffusion agrees with simulations in PyBoltz across a range of operating pressures (200–1500 Torr). These results demonstrate that a Q-Pix readout can successfully reconstruct the ionization topology in a TPC.

47 OTHER INSTRUMENTATION↗
DOE OSTI2026

High-resolution modeling of indoor radon exposure with uncertainty quantification in Utah

Indoor radon accounts for 37% of population-level exposure to ionizing radiation in the United States. However, radon metrics are typically reported at coarse spatial scales, potentially obscuring meaningful local variation. We developed a high-resolution modeling framework to estimate indoor radon concentrations across Utah while explicitly quantifying predictive uncertainty. A total of 19,497 residential radon measurements collected between 2006 and 2017 were combined with environmental and housing characteristics and analyzed using a geospatial neural network that accommodates spatial dependence and nonlinear associations. Predictions were generated on a uniform hexagonal grid at 0.73 km2 resolution (H3 level 8). Out-of-sample predictions aggregated to the H3 level 8 grid showed good agreement with observed concentrations (Pearson r=0.64), while household-level predictions exhibited more moderate agreement (r=0.45). The model produced well-calibrated uncertainty estimates, with 24.1% of held-out observations exceeding the predicted 75th-percentile threshold. Maps of predicted radon concentrations and the probability of exceeding the U.S. EPA action level of 148 Bq/m3 (4 pCi/L) revealed substantial fine-scale spatial heterogeneity that was not apparent in conventional coarse-resolution summaries, with greater local variability observed in densely monitored urban counties than in sparsely sampled regions. High-resolution radon models that explicitly quantify uncertainty provide a useful framework for characterizing the spatial distribution of indoor radon and identifying areas of elevated exceedance risk. These findings highlight the value of fine-scale monitoring data and uncertainty-aware modeling approaches for radon exposure assessment, environmental risk characterization, and radon-related health research.

Wu, Yunhan [ORNL] (ORCID:0000000178842994)↗
DOE OSTI2018

Probing the predissociated levels of the S 1 state of acetylene via H-atom fluorescence and photofragment fluorescence action spectroscopy

Here, we report two new experimental schemes to obtain rotationally resolved high-resolution spectra of predissociated S 1 acetylene levels in the 47 000-47 300 cm -1 energy region (~1200 cm -1 above the predissociation threshold). The two new detection schemes are compared to several other detection schemes (employed at similar laser power, molecular beam temperature, and number of signal averages) that have been used in our laboratory to study predissociated S 1 acetylene levels, both in terms of the signal-to-noise ratio (S/N) of the resultant spectra and experimental simplicity. In the first method, H-atoms from the predissociated S 1 acetylene levels are probed by two-photon laser-induced fluorescence (LIF). The H-atoms are pumped to the 3d level by the two-photon resonance transition at 205.14 nm. The resulting 3d–2p fluorescence (654.5 nm) is collected by a photomultiplier. The S/N of the H-atom fluorescence action spectrum is consistently better by ~3× than that of the more widely used H-atom resonance-enhanced multiphoton ionization (REMPI) detection. Laser alignment is also considerably easier in H-atom fluorescence detection than H-atom REMPI detection due to the larger number-density of molecules that can be used in fluorescence vs. REMPI detection schemes. In the second method, fluorescence from electronically excited C 2 and C 2 H photofragments of S 1 acetylene is detected. In contrast to the H-atom detection schemes, the detected C 2 and C 2 H photofragments are produced by the same UV laser as is used for the ÖX acetylene excitation. As a result, laser alignment is greatly simplified for the photofragment fluorescence detection scheme, compared to both H-atom detection schemes. Using the photofragment fluorescence detection method, we are able to obtain action spectra of predissociated S 1 acetylene levels with S/N ~2× better than the HCCH REMPI detection and ~10× better than H-atom and HCCH LIF detection schemes.

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

Observation of a π-Type Dipole-Bound State in Molecular Anions

We report the observation of a π-type dipole-bound state (π-DBS) in cryogenically cooled deprotonated 9-anthrol molecular anions (9AT – ) by resonant two-photon photoelectron imaging. A DBS is observed 191 cm –1 (0.0237 eV) below the detachment threshold, and the existence of the π-DBS is revealed by a distinct (s + d)-wave photoelectron angular distribution. The π-DBS is stabilized by the large anisotropic in-plane polarizability of 9AT. Here, the population of the dipole-forbidden π-DBS is proposed to be via a nonadiabatic coupling with the dipole-allowed σ-type DBS mediated by molecular rotations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

SiPM-matrix readout of two-phase argon detectors using electroluminescence in the visible and near infrared range

Proportional electroluminescence (EL) in noble gases is used in two-phase detectors for dark matter searches to record (in the gas phase) the ionization signal induced by particle scattering in the liquid phase. The “standard” EL mechanism is considered to be due to noble gas excimer emission in the vacuum ultraviolet (VUV). In addition, there are two alternative mechanisms, producing light in the visible and near infrared (NIR) ranges. The first is due to bremsstrahlung of electrons scattered on neutral atoms (“neutral bremsstrahlung”, NBrS). The second, responsible for electron avalanche scintillation in the NIR at higher electric fields, is due to transitions between excited atomic states. In this work, we have for the first time demonstrated two alternative techniques of the optical readout of two-phase argon detectors, in the visible and NIR range, using a silicon photomultiplier matrix and electroluminescence due to either neutral bremsstrahlung or avalanche scintillation. The amplitude yield and position resolution were measured for these readout techniques, which allowed to assess the detection threshold for electron and nuclear recoils in two-phase argon detectors for dark matter searches. To the best of our knowledge, this is the first practical application of the NBrS effect in detection science.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

Communication: Protonation process of formic acid from the ionization and fragmentation of dimers induced by synchrotron radiation in the valence region

The ionization and fragmentation of monomers of organic molecules have been extensively studied in the gas phase using mass spectroscopy. In the spectra of these molecules it is possible to identify the presence of protonated cations, which have a mass-to-charge ratio one unit larger than the parent ion. In this work, we investigate this protonation process as a result of dimers photofragmentation. Experimental photoionization and photofragmentation results of doubly deuterated formic acid (DCOOD) in the gas phase by photons in the vacuum ultraviolet region are presented. The experiment was performed by using a time-of-flight mass spectrometer installed at the Brazilian Synchrotron Light Laboratory and spectra for different pressure values in the experimental chamber were obtained. The coupled cluster approach with single and double substitutions was employed to assist the experimental analysis. Results indicate that protonated formic acid ions are originated from dimer dissociation, and the threshold photoionization of (DCOOD)⋅D{sup +} is also determined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory

Methacrolein oxide (MACR-oxide) is a four-carbon, resonance-stabilized Criegee intermediate produced from isoprene ozonolysis, yet its reactivity is not well understood. This study identifies the functionalized hydroperoxide species, 1-hydroperoxy-2-methylallyl formate (HPMAF), generated from the reaction of MACR-oxide with formic acid using multiplexed photoionization mass spectrometry (MPIMS, 298 K = 25 °C, 10 torr = 13.3 hPa). Electronic structure calculations indicate the reaction proceeds via an energetically favorable 1,4-addition mechanism. The formation of HPMAF is observed by the rapid appearance of a fragment ion at m/z 99, consistent with the proposed mechanism and characteristic loss of HO2 upon photoionization of functional hydroperoxides. The identification of HPMAF is confirmed by comparison of the appearance energy of the fragment ion with theoretical predictions of its photoionization threshold. The results are compared to analogous studies on the reaction of formic acid with methyl vinyl ketone oxide (MVK-oxide), the other four-carbon Criegee intermediate in isoprene ozonolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗