Vacuum ultraviolet photoionization cross section of the hydroxyl radical

The absolute photoionization spectrum of the hydroxyl (OH) radical from 12.513 to 14.213 eV was measured by multiplexed photoionization mass spectrometry with time-resolved radical kinetics. Tunable vacuum ultraviolet (VUV) synchrotron radiation was generated at the Advanced Light Source. OH radicals were generated from the reaction of O(^1D) + H_2O in a flow reactor in He at 8 Torr. The initial O(^1D) concentration, where the atom was formed by pulsed laser photolysis of ozone, was determined from the measured depletion of a known concentration of ozone. Concentrations of OH and O(^3P) were obtained by fitting observed time traces with a kinetics model constructed with literature rate coefficients. The absolute cross section of OH was determined to be σ(13.436 eV) = 3.2 ± 1.0 Mb and σ(14.193 eV) = 4.7 ± 1.6 Mb relative to the known cross section for O(^3P) at 14.193 eV. The absolute photoionization spectrum was obtained by recording a spectrum at a resolution of 8 meV (50 meV steps) and scaling to the single-energy cross sections. We computed the absolute VUV photoionization spectrum of OH and O(^3P) using equation-of-motion coupled-cluster Dyson orbitals and a Coulomb photoelectron wave function and found good agreement with the observed absolute photoionization spectra

VUV Photoionization Cross Sections of HO_2, H_2O_2, and H_2CO

The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO_2), hydrogen peroxide (H_2O_2), and formaldehyde (H_2CO) have been measured from their first ionization thresholds to 12.008 eV. HO_2, H_2O_2, and H_2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl_2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO_2, H_2O_2, and H_2CO on an absolute scale, resulting in absolute photoionization spectra

Vacuum ultraviolet photoionization cross section of the hydroxyl radical

The absolute photoionization spectrum of the hydroxyl (OH) radical from 12.513 to 14.213 eV was measured by multiplexed photoionization mass spectrometry with time-resolved radical kinetics. Tunable vacuum ultraviolet (VUV) synchrotron radiation was generated at the Advanced Light Source. OH radicals were generated from the reaction of O(^1D) + H_2O in a flow reactor in He at 8 Torr. The initial O(^1D) concentration, where the atom was formed by pulsed laser photolysis of ozone, was determined from the measured depletion of a known concentration of ozone. Concentrations of OH and O(^3P) were obtained by fitting observed time traces with a kinetics model constructed with literature rate coefficients. The absolute cross section of OH was determined to be σ(13.436 eV) = 3.2 ± 1.0 Mb and σ(14.193 eV) = 4.7 ± 1.6 Mb relative to the known cross section for O(^3P) at 14.193 eV. The absolute photoionization spectrum was obtained by recording a spectrum at a resolution of 8 meV (50 meV steps) and scaling to the single-energy cross sections. We computed the absolute VUV photoionization spectrum of OH and O(^3P) using equation-of-motion coupled-cluster Dyson orbitals and a Coulomb photoelectron wave function and found good agreement with the observed absolute photoionization spectra

Time-resolved measurements of product formation in the low-temperature (550-675 K) oxidation of neopentane : a probe to investigate chain-branching mechanism

Product formation, in particular ketohydroperoxide formation and decomposition, were investigated in time-resolved, Cl-atom initiated neopentane oxidation experiments in the temperature range 550-675 K using a photoionization time-of-flight mass spectrometer. Ionization light was provided either by Advanced Light Source tunable synchrotron radiation or similar to 10.2 eV fixed energy radiation from a H-2-discharge lamp. Experiments were performed both at 1-2 atm pressure using a high-pressure reactor and also at similar to 9 Torr pressure employing a low-pressure reactor for comparison. Because of the highly symmetric structure of neopentane, ketohydroperoxide signal can be attributed to a 3-hydroperoxy-2,2-dimethylpropanal isomer, i.e. from a gamma-ketohydroperoxide (gamma-KHP). The photoionization spectra of the gamma-KHP measured at low-and high pressures and varying oxygen concentrations agree well with each other, further supporting they originate from the single isomer. Measurements performed in this work also suggest that the "Korcek" mechanism may play an important role in the decomposition of 3-hydroperoxy-2,2-dimethylpropanal, especially at lower temperatures. However, at higher temperatures where gamma-KHP decomposition to hydroxyl radical and oxy-radical dominates, oxidation of the oxy-radical yields a new important channel leading to acetone, carbon monoxide, and OH radical. Starting from the initial neopentyl + O-2 reaction, this channel releases altogether three OH radicals. A strongly temperature-dependent reaction product is observed at m/z = 100, likely attributable to 2,2-dimethylpropanedial.Peer reviewe

Direct Measurements of Unimolecular and Bimolecular Reaction Kinetics of the Criegee Intermediate (CH 3 ) 2 COO

The Criegee intermediate acetone oxide, (CH3)2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10–11 cm3 s–1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10–10 cm3 s–1 at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH3CHOO with SO2, and in good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N2 from cavity ring-down decay of the ultraviolet absorption of (CH3)2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10–10 to (2.29 ± 0.08) × 10–10 cm3 s–1. Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10–12 cm3 s–1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH3CHOO with NO2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH3)2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s–1, is similar to determinations from ozonolysis. The present measurements confirm the large rate coefficient for reaction of (CH3)2COO with SO2 and the small rate coefficient for its reaction with water. Product measurements of the reactions of (CH3)2COO with NO2 and with SO2 suggest that these reactions may facilitate isomerization to 2-hydroperoxypropene, possibly by subsequent reactions of association products

Direct kinetics study of CH2OO + methyl vinyl ketone and CH2OO + methacrolein reactions and an upper limit determination for CH2OO + CO reaction

Methyl vinyl ketone (MVK) and methacrolein (MACR) are important intermediate products in atmospheric degradation of volatile organic compounds, especially of isoprene. This work investigates the reactions of the smallest Criegee intermediate, CH2OO, with its co-products from isoprene ozonolysis, MVK and MACR, using multiplexed photoionization mass spectrometry (MPIMS), with either tunable synchrotron radiation from the Advanced Light Source or Lyman-alpha (10.2 eV) radiation for photoionization. CH2OO was produced via pulsed laser photolysis of CH(2)l(2) in the presence of excess O-2. Time-resolved measurements of reactant disappearance and of product formation were performed to monitor reaction progress; first order rate coefficients were obtained from exponential fits to the CH2OO decays. The bimolecular reaction rate coefficients at 300 K and 4 Torr are k(CH2OO + MVK) = (5.0 +/- 0.4) x 10(-13) cm(3) s(-1) and k(CH2OO + MACR) = (4.4 +/- 1.0) x 10(-13) cm(3) s(-1), where the stated +/- 2 sigma uncertainties are statistical uncertainties. Adduct formation is observed for both reactions and is attributed to the formation of a secondary ozonides (1,2,4-trioxolanes), supported by master equation calculations of the kinetics and the agreement between measured and calculated adiabatic ionization energies. Kinetics measurements were also performed for a possible bimolecular CH2OO + CO reaction and for the reaction of CH2OO with CF3CHCH2 at 300 K and 4 Torr. For CH2OO + CO, no reaction is observed and an upper limit is determined: k(CH2OO + CO) <2 x 10(-16) cm(3) s(-1). For CH2OO + CF3CHCH2, an upper limit of k(CH2OO + CF3CHCH2) <2 x 10(-14) cm(3) s(-1) is obtained.Peer reviewe

Проектирование расписания движения городского пассажирского транспорта на основе одноприборной задачи теории расписания

The branched C alcohol isopentanol (3-methylbutan-1-ol) has shown promise as a potential biofuel both because of new advanced biochemical routes for its production and because of its combustion characteristics, in particular as a fuel for homogeneous-charge compression ignition (HCCI) or related strategies. In the present work, the fundamental autoignition chemistry of isopentanol is investigated by using the technique of pulsed-photolytic Cl-initiated oxidation and by analyzing the reacting mixture by time-resolved tunable synchrotron photoionization mass spectrometry in low-pressure (8 Torr) experiments in the 550-750 K temperature range. The mass-spectrometric experiments reveal a rich chemistry for the initial steps of isopentanol oxidation and give new insight into the low-temperature oxidation mechanism of medium-chain alcohols. Formation of isopentanal (3-methylbutanal) and unsaturated alcohols (including enols) associated with HO production was observed. Cyclic ether channels are not observed, although such channels dominate OH formation in alkane oxidation. Rather, products are observed that correspond to formation of OH via β-C-C bond fission pathways of QOOH species derived from β- and γ-hydroxyisopentylperoxy (RO ) radicals. In these pathways, internal hydrogen abstraction in the RO QOOH isomerization reaction takes place from either the -OH group or the C-H bond in α-position to the -OH group. These pathways should be broadly characteristic for longer-chain alcohol oxidation. Isomer-resolved branching ratios are deduced, showing evolution of the main products from 550 to 750 K, which can be qualitatively explained by the dominance of RO chemistry at lower temperature and hydroxyisopentyl decomposition at higher temperature

Perspective on Mechanism Development and Structure‐Activity Relationships for Gas‐Phase Atmospheric Chemistry

This perspective gives our views on general aspects and future directions of gas‐phase atmospheric chemical kinetic mechanism development, emphasizing on the work needed for the sustainable development of chemically detailed mechanisms that reflect current kinetic, mechanistic, and theoretical knowledge. Current and future mechanism development efforts and research needs are discussed, including software‐aided autogeneration and maintenance of kinetic models as a future‐proof approach for atmospheric model development. There is an overarching need for the evaluation and extension of structure‐activity relationships (SARs) that predict the properties and reactions of the many multifunctionalized compounds in the atmosphere that are at the core of detailed mechanisms, but for which no direct chemical data are available. Here, we discuss the experimental and theoretical data needed to support the development of mechanisms and SARs, the types of SARs relevant to atmospheric chemistry, the current status and limitations of SARs for various types of atmospheric reactions, the status of thermochemical estimates needed for mechanism development, and our outlook for the future. The authors have recently formed a SAR evaluation working group to address these issues

An experimental probe of electronic interactions in excited molecules produced by charge exchange

The electronic structure and fundamental electronic interactions of sym-triazine, HN₂, and HOCO were probed using translational spectroscopy coupled with coincidence detection techniques. The neutral species were prepared in excited vibronic states by neutralization of the corresponding parent cation with cesium, and full kinematic descriptions of the resulting dissociation dynamics were measured and used as a basis for identifying the accessed states and describing the mechanisms leading to dissociation. This dissertation begins with a brief introduction to the production of neutral species via neutralization with cesium, followed by a general overview of the experimental apparatus and data analysis methods. The dissertation concludes with detailed accounts of the experiments performed on sym-triazine, HN₂, and HOCO. A rich history of mechanistic debate is associated with the dissociation of sym-triazine. A collaborative experimental and theoretical investigation into the three-body dissociation dynamics (sym-triazine$$right arrow$$3HCN) resulting from excitation of sym-triazine into the $$pi$$*$$left arrow$$n and 3s Rydberg electronic manifolds established the working theory and treatment of experimental data that was carried over to later experiments. It was found that the topology of the electronic manifold into which sym-triazine is excited is consistent with the observed dissociation mechanism; sym- triazine dissociates to 3HCN via a concerted mechanism when excited to the highly symmetric $$pi$$*$$left arrow$$n electronic manifold, and via a stepwise mechanism when produced in the Jahn-Teller distorted 3s Rydberg electronic manifold. A two-body channel ($$right arrow$$HCN+ C₂N₂H₂) was also observed, and shares many correlations with the stepwise three-body dissociation mechanism. HN₂ and HOCO are reaction intermediates in important physical processes, and were both studied alongside their deuterated isotopologs to aid interpretation of the observed dissociation dynamics. HN₂ is believed to be a transient intermediate in thermal De-NOx processes, but has thus far eluded direct experimental detection. The CE experiments described here accessed three different dissociative vibronic states of HN₂ and use the observed dissociation dynamics to describe possible interactions between potential energy surfaces that ultimately lead to H/D+N₂ products. HOCO is a transient reaction intermediate in combustion processes, and, similar to HN₂, is difficult to isolate for spectroscopic investigation. The study described in this dissertation marks the first direct probe of excited electronic states of this species and describes possible mechanisms leading from the 1² A" electronic state of trans-HOCO to the observed H/D+CO₂ and OH/OD+CO product channels