Absolute Rate Coefficients Research Articles

Rate coefficients for the gas‐phase reaction of OH radicals with the L4, L5, D5, and D6 permethylsiloxanes

AbstractRate coefficients, k(T), for the gas‐phase OH radical reaction with decamethyltetrasiloxane ((CH3)3SiO[Si(CH3)2O]2Si(CH3)3, L4, k1), dodecamethylpentasiloxane ((CH3)3SiO[Si(CH3)2O]3Si(CH3)3, L5, k2), and decamethylcyclopentasiloxane ([–Si(CH3)2O–]5, D5, k3), and dodecamethylcyclohexasiloxane ([–Si(CH3)2O–]6, D6, k4) were measured using a pulsed laser photolysis—laser induced fluorescence absolute method over the temperature range 270–370 K. The obtained room temperature rate coefficients, with quoted 2σ absolute uncertainties, and fitted temperature dependence are (cm−3 molecule−1 s−1): The 2σ absolute rate coefficient uncertainty, for all compounds included in this study, is conservatively estimated to be ∼10% over the entire temperature range. The cyclic permethylsiloxanes were found to be less reactive than the analogous linear compound, while both linear and cyclic compounds show increasing reactivity with increasing number of CH3‐ groups. A structure activity relationship (SAR) parameterization for the permethylsiloxanes is presented. The estimated atmospheric lifetimes due to OH reaction for L4, L5, D5, and D6 are 5.2, 4.4, 6.8, and 5.2 days, respectively.

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In order to establish important reaction properties, such as rate coefficients, it is often necessary to know the number of reactants that are present in an interaction region. The absolute number densities of pulsed supersonic molecular (NH3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document}) and atomic (H) beams are reported using a laser-based detection method, under a range of experimental conditions including photolysis, Zeeman deceleration, and magnetic focusing. Time-averaged densities of (3.6 ± 2.7) ×\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ imes $$\\end{document} 104\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^4$$\\end{document} cm-3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{-3}$$\\end{document} are reported for successfully Zeeman-decelerated and magnetically focused H atoms, generated by the photodissociation of precursor NH3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document} molecules. Without the magnetic guide components in the beamline, the density of the target radicals of interest is somewhat lower, at (2.5 ± 1.8) ×\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ imes $$\\end{document} 104\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^4$$\\end{document} cm-3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{-3}$$\\end{document}. The average density of the undecelerated H atom beam is approximately an order of magnitude higher (2.9 ± 1.9) ×\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ imes $$\\end{document} 105\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^5$$\\end{document} cm-3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{-3}$$\\end{document}, with the average density of the molecular ammonia beam over two orders of magnitude higher again (5.1 ± 2.9) ×\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ imes $$\\end{document} 107\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^7$$\\end{document} cm-3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{-3}$$\\end{document}. The average number densities measured for the two different species of interest in this work span more than three orders of magnitude. These findings highlight the need for accurate and precise experimental measurements of number densities—for each species of interest, under the appropriate experimental conditions—before doing absolute rate coefficient calculations.Graphical abstract

The Environmental Pollutant NO3⋅ Rapidly Damages Alkene Moieties in Lipids Through Electron Transfer

AbstractThe presence of alkene moieties in fatty acids of (phospho)lipids and cholesterol derivatives makes them highly susceptible to damage by nitrate radicals (NO3⋅), potentially formed through simultaneous exposure to the environmental air pollutants nitrogen dioxide (NO2⋅) and ozone (O3). Absolute rate coefficients derived from reactions with simplified model systems range from 4 to 8×109 M−1 s−1 in acetonitrile, ranking among the highest determined for NO3⋅ reactions with biomolecules in solution to date. Alkenes featuring an electron‐withdrawing carbonyl substituent also display notable reactivity with k values of (2.5±1.0)×108 M−1 s−1. Calculations suggest that these reactions are initiated by oxidative electron transfer (ET) involving the C=C bond, followed by recombination of the resulting alkene radical cation with nitrate anion (NO3−) to form the nitrate adduct radical as the kinetically controlled product. Conversely, saturated fatty acid derivatives and cholestanol react with NO3⋅ through hydrogen atom transfer (HAT) with rate coefficients of 106–107 M−1 s−1, indicating that biomolecules with a considerable number of non‐ or moderately activated sp3 C−H bonds are also highly susceptible to NO3⋅ attack. These findings underscore the potential health hazards associated with exposure to combined NO2⋅ and O3 gases.

Merged-Beams Study of the Reaction of Cold HD+ with C Atoms Reveals a Pronounced Intramolecular Kinetic Isotope Effect

We present a merged-beams study of reactions between HD+ ions, stored in the Cryogenic Storage Ring (CSR), and laser-produced ground-term C atoms. The molecular ions are stored for up to 20 s in the extreme vacuum of the CSR, where they have time to relax radiatively until they reach their vibrational ground state (within 0.5 s of storage) and rotational states with J≤3 (after 5 s). We combine our experimental studies with quasiclassical trajectory calculations based on two reactive potential energy surfaces. In contrast to previous studies with internally excited H2+ and D2+ ions, our results reveal a pronounced isotope effect, favoring the production of CH+ over CD+ across all collision energies, and a significant increase in the absolute rate coefficient of the reaction. Our experimental results agree well with our theoretical calculations for vibrationally relaxed HD+ ions in their lowest rotational states. Published by the American Physical Society 2024

Absolute rate coefficient measurements of the reactions of vibrationally cold HD+ and H3+ ions with neutral C atoms

Ion-neutral reactions are driving the formation of small molecules in the gas phase of interstellar clouds, where hydrogen molecules and their ions are by far the most important collision partners for any species in the astrochemical network. Here we present absolute rate coefficient measurements for the reactions HD++C→CH+/CD++D/H and H3++C→CH+/CH2++H2/H obtained using a recently commissioned ion-neutral collision setup at the Cryogenic Storage Ring. Our measurements with vibrationally cold ions result in significantly higher rate coefficients when compared with previous studies using internally excited ions, bringing them in better agreement with classical capture theories. Moreover, we have performed detailed quasiclassical trajectory (QCT) calculations for the HD++C reaction, using new potential energy surfaces. Our experimental results and the QCT calculations show very good agreement for the absolute cross section of the reactions, as well as for the isotope effect. These results have great potential relevance for the chemistry of the interstellar medium and the onset of organic chemistry in space. Published by the American Physical Society 2024

Spirometry test values can be estimated from a single chest radiograph.

Physical measurements of expiratory flow volume and speed can be obtained using spirometry. These measurements have been used for the diagnosis and risk assessment of chronic obstructive pulmonary disease and play a crucial role in delivering early care. However, spirometry is not performed frequently in routine clinical practice, thereby hindering the early detection of pulmonary function impairment. Chest radiographs (CXRs), though acquired frequently, are not used to measure pulmonary functional information. This study aimed to evaluate whether spirometry parameters can be estimated accurately from single frontal CXR without image findings using deep learning. Forced vital capacity (FVC), forced expiratory volume in 1 s (FEV1), and FEV1/FVC as spirometry measurements as well as the corresponding chest radiographs of 11,837 participants were used in this study. The data were randomly allocated to the training, validation, and evaluation datasets at an 8:1:1 ratio. A deep learning network was pretrained using ImageNet. The input and output information were CXRs and spirometry test values, respectively. The training and evaluation of the deep learning network were performed separately for each parameter. The mean absolute error rate (MAPE) and Pearson's correlation coefficient (r) were used as the evaluation indices. The MAPEs between the spirometry measurements and AI estimates for FVC, FEV1 and FEV1/FVC were 7.59% (r = 0.910), 9.06% (r = 0.879) and 5.21% (r = 0.522), respectively. A strong positive correlation was observed between the measured and predicted indices of FVC and FEV1. The average accuracy of >90% was obtained in each estimation of spirometry indices. Bland-Altman analysis revealed good agreement between the estimated and measured values for FVC and FEV1. Frontal CXRs contain information related to pulmonary function, and AI estimation performed using frontal CXRs without image findings could accurately estimate spirometry values. The network proposed for estimating pulmonary function in this study could serve as a recommendation for performing spirometry or as an alternative method, suggesting its utility.

Atmospheric oxidation of new “green” solvents – Part 2: methyl pivalate and pinacolone

Abstract. Lab-based experimental and computational methods were used to study the atmospheric degradation of two promising “green” solvents: pinacolone, (CH3)3CC(O)CH3, and methyl pivalate, (CH3)3CC(O)OCH3. Pulsed laser photolysis coupled to pulsed laser-induced fluorescence was used to determine absolute rate coefficients (in 10−12 cm3 molec.−1 s−1) of k1(297 K) = (1.2 ± 0.2) for OH + (CH3)3CC(O)CH3 (Reaction R1) and k2(297 K) = (1.3 ± 0.2) for OH + (CH3)3CC(O)OCH3 (Reaction R2), in good agreement with one previous experimental study. Rate coefficients for both reactions were found to increase at elevated temperature, with k1(T) adequately described by k1(297–485 K) = 2.1 × 10−12 exp(-200/T) cm3 molec.−1 s−1. k2(T) exhibited more complex behaviour, with a local minimum at around 300 K. In the course of this work, k3(295–450 K) was obtained for the well-characterised reaction OH + C2H5OH (ethanol; Reaction R3), in satisfactory agreement with the evaluated literature. UV–Vis spectroscopy experiments and computational calculations were used to explore cross-sections for (CH3)3CC(O)CH3 photolysis (Reaction R4), while (CH3)3CC(O)OCH3 showed no sign of absorption over the wavelengths of interest. Absorption cross-sections for (CH3)3CC(O)CH3, σ4(λ), in the actinic region were larger, and the maximum was red-shifted compared to estimates (methyl ethyl ketone (MEK) values) used in current state-of-science models. As a consequence, we note that photolysis (Reaction R4) is likely the dominant pathway for removal of (CH3)3CC(O)CH3 from the troposphere. Nonetheless, large uncertainties remain as quantum yields φ4(λ) remain unmeasured. Lifetime estimates based upon Reactions (R1) and (R4) span the range 2–9 d and are consequently associated with a poorly constrained estimated photochemical ozone creation potential (POCPE). In accord with previous studies, (CH3)3CC(O)OCH3 did not absorb in the actinic region, allowing for straightforward calculation of an atmospheric lifetime of ≈ 9 d and a small POCPE ≈ 11.

Room temperature rate coefficients for the reaction of chlorine atoms with a series of volatile methylsiloxanes (L2‐L5, D3‐D6)

AbstractThe kinetics of chlorine (Cl) atom reactions with a series of volatile methylsiloxanes (VMS) including hexamethyldisiloxane (L2), octamethyltrisiloxane (L3), decamethyltetrasiloxane (L4), dodecamethylpentasiloxane (L5), hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were investigated in relative rate experiments at room temperature and atmospheric pressure. The experiments were carried out in a 0.2 m3 PFA Teflon chamber, employing proton‐transfer‐reaction time‐of‐flight mass spectrometry (PTR‐ToF‐MS) as the chemical‐analytical tool. The following relative and absolute reaction rate coefficients were obtained using isoprene as reference compound (kVMS/kisoprene; kVMS × 1010 cm3 molec−1 s −1): L2 (0.32 ± 0.02; 1.31 ± 0.21), L3 (0.38 ± 0.00; 1.56 ± 0.23), L4 (0.48 ± 0.01; 1.98 ± 0.29), L5 (0.54 ± 0.03; 2.22 ± 0.34), D3 (0.14 ± 0.02; 0.56 ± 0.13), D4 (0.26 ± 0.01; 1.05 ± 0.16), D5 (0.36 ± 0.02; 1.46 ± 0.22), D6 (0.39 ± 0.02; 1.61 ± 0.25). The following relative and absolute reaction rate coefficients were obtained using toluene as reference compound (kVMS/ktoluene; kVMS × 1010 cm3 molec−1 s −1): L2 (1.59 ± 0.18; 0.95 ± 0.14), L3 (2.25 ± 0.14; 1.35 ± 0.16), L4 (2.38 ± 0.01; 1.43 ± 0.14), L5 (3.57 ± 0.11; 2.14 ± 0.22), D3 (0.87 ± 0.01; 0.52 ± 0.05), D4 (1.48 ± 0.12; 0.89 ± 0.11), D5 (2.02 ± 0.15; 1.21 ± 0.15), D6 (2.54 ± 0.11; 1.52 ± 0.17). Our data confirm that reactions with Cl atoms need to be taken into account when assessing the decomposition of VMS in Cl‐rich tropospheric environments.

Near-thermo-neutral electron recombination of titanium oxide ions.

While the dissociative recombination (DR) of ground-state molecular ions with low-energy free electrons is generally known to be exothermic, it has been predicted to be endothermic for a class of transition-metal oxide ions. To understand this unusual case, the electron recombination of titanium oxide ions (TiO+) with electrons has been experimentally investigated using the Cryogenic Storage Ring. In its low radiation field, the TiO+ ions relax internally to low rotational excitation (≲100 K). Under controlled collision energies down to ∼2 meV within the merged electron and ion beam configuration, fragment imaging has been applied to determine the kinetic energy released to Ti and O neutral reaction products. Detailed analysis of the fragment imaging data considering the reactant and product excitation channels reveals an endothermicity for the TiO+ dissociative electron recombination of (+4 ± 10) meV. This result improves the accuracy of the energy balance by a factor of 7 compared to that found indirectly from hitherto known molecular properties. Conversely, the present endothermicity yields improved dissociation energy values for D0(TiO) = (6.824 ± 0.010)eV and D0(TiO+) = (6.832 ± 0.010)eV. All thermochemistry values were compared to new coupled-cluster calculations and found to be in good agreement. Moreover, absolute rate coefficients for the electron recombination of rotationally relaxed ions have been measured, yielding an upper limit of 1 × 10-7 cm3 s-1 for typical conditions of cold astrophysical media. Strong variation of the DR rate with the TiO+ internal excitation is predicted. Furthermore, potential energy curves for TiO+ and TiO have been calculated using a multi-reference configuration interaction method to constrain quantum-dynamical paths driving the observed TiO+ electron recombination.

Absolute dielectronic recombination rate coefficients of highly charged ions at the storage ring CSRm and CSRe

Dielectronic recombination (DR) is one of the dominant electron–ion recombination mechanisms for most highly charged ions (HCIs) in cosmic plasmas, and thus, it determines the charge state distribution and ionization balance therein. To reliably interpret spectra from cosmic sources and model the astrophysical plasmas, precise DR rate coefficients are required to build up an accurate understanding of the ionization balance of the sources. The main cooler storage ring (CSRm) and the experimental cooler storage ring (CSRe) at the Heavy-Ion Research Facility in Lanzhou (HIRFL) are both equipped with electron cooling devices, which provide an excellent experimental platform for electron-ion collision studies for HCIs. Here, the status of the DR experiments at the HIRFL-CSR is outlined, and the DR measurements with Na-like Kr25+ ions at the CSRm and CSRe are taken as examples. In addition, the plasma recombination rate coefficients for Ar12+, 14+, Ca14+, 16+, 17+, Ni19+, and Kr25+ ions obtained at the HIRFL-CSR are provided. All the data presented in this paper are openly available at https://doi.org/10.57760/sciencedb.j00113.00092.

Experimental and Theoretical Investigation of Reactions of Formyl (HCO) Radicals in the Gas Phase: (I) Kinetics of HCO Radicals with Ethyl Formate and Ethyl Acetate in Tropospherically Relevant Conditions.

Formyl (HCO) radicals were generated in situ in the gas phase via the photolysis of glyoxal in N2 at 248 nm using the pulsed laser photolysis-cavity ring-down spectrometry technique, and the absorption cross-section of the radical was measured to be σHCO = (5.3 ± 0.9) × 10-19 cm2 molecule-1 at 298 K and 615.75 nm, which was the probing wavelength. The kinetics of the reactions of HCO radicals with ethyl formate (EF) and ethyl acetate (EA) were investigated experimentally in the temperature range of 260-360 (±2) K at a pressure of 60 Torr/N2. The absolute rate coefficient for the reaction between HCO and EF was measured to be (298 K) = (1.39 ± 0.30) × 10-14 cm3 molecule-1 s-1 at ambient temperature, whereas that for the reaction of HCO with EA was measured tobe (298 K) = (2.05 ± 0.43) × 10-14 cm3 molecule-1 s-1. The reaction of HCO with EA was faster than that with EF, which might be due to the greater stability of the formed radical intermediate due to hyperconjugative and inductive effects. The dependency of the measured kinetics on experimental pressures and laser fluences was examined within a certain range. To complement the experiments, kinetics of the title reactions in the temperature range of 200-400 K were deciphered theoretically via the canonical variational transition-state theory with small-curvature tunneling and interpolated single-point energy (CVT/SCT/ISPE) method using a dual-level approach at the CCSD(T)/cc-pVTZ//MP2/6-311++G(d,p) level of theory/basis set. A good degree of agreement was detected between the rate coefficients measured experimentally and those calculated theoretically both at room temperature and throughout the range of temperatures studied. The kinetic branching ratios and thermochemistry of the reactions were investigated to understand the thermodynamic feasibility and kinetic lability of each pathway throughout the studied temperatures. Atmospheric implications of these reactions of HCO radicals are also discussed.

Investigation of the Gas-Phase Reaction of Nopinone with OH Radicals: Experimental and Theoretical Study

Monoterpenes are the most essential reactive biogenic volatile organic compounds. Their removal from the atmosphere leads to the formation of oxygenated compounds, such as nopinone (C9H14O), one of the most important first-generation β-pinene oxidation products that play a pivotal role in environmental and biological applications. In this study, experimental and theoretical rate coefficients were determined for the gas-phase reaction of nopinone with hydroxyl radicals (OH). The absolute rate coefficient was measured for the first time using a cryogenically cooled cell along with the pulsed laser photolysis–laser-induced fluorescence technique at 298 K and 7 Torr. The hydrogen abstraction pathways were found by using electronic structure calculations to determine the most favourable H-abstraction position. Pathway 5 (bridgehead position) was more favourable, with a small barrier height of −1.23 kcal/mol. The rate coefficients were calculated based on the canonical variational transition state theory with the small-curvature tunnelling method (CVT/SCT) as a function of temperature. The average experimental rate coefficient (1.74 × 10−11 cm3 molecule−1 s−1) was in good agreement with the theoretical value (2.2 × 10−11 cm3 molecule−1 s−1). Conclusively, the results of this study pave the way to understand the atmospheric chemistry of nopinone with OH radicals.

Correlation in quantum chemical calculation and its effect on the uncertainty of theoretically predicted rate coefficients and branching ratios

The transition state theory (TST) and RRKM/master equation (ME) method have been well acknowledged in developing combustion models. Uncertainties in input parameters, such as energies and vibrational frequencies which are produced from quantum chemical computations, largely contribute to uncertainties of the theoretically predicted rate coefficients. The potential correlations among these parameters and their effects on the uncertainty of rate coefficients have been investigated in the present work. The correlations in quantum chemical computations on H abstraction, H addition and thermal decomposition reactions, regarding radical sites, molecular types and reaction types are investigated and quantified using Pearson correlation coefficients. The results show that notable correlations exist in energies and imaginary frequencies. The correlation factors are then incorporated into the global uncertainty analysis for two typical TST and RRKM/ME computation systems, i.e., H abstraction reactions of acetaldehyde by the HO2 radical (TST) and the multi-well multi-channel reactions on the C4H7 potential energy surface (RRKM/ME) to unravel the effects of correlation on the uncertainties of rate coefficients and branching ratios. Comparing with the random independent sampling for input parameters, to include correlations among input parameters largely reduces the predicted uncertainties, with the largest reduction of ∼30% for absolute rates and ∼45% for the branching ratio in TST calculations and ∼33% for absolute rates and ∼50% for branching ratios in RRKM/ME calculations. The uncertainty propagation behavior with and without considering the correlation in the input parameters was further uncovered by the sensitivity analysis. In the TST calculation, the uncertainty reduction for absolute rate coefficients solely originates from the reduction of the sampling space, and the uncertainty reduction for the branching ratio originates from both the reduced parameter space and the cancelation of sensitive parameters. In the RRKM/ME calculation, the uncertainty reduction in rate coefficients arises only from reduced sampling space, but the uncertainty reduction in branching ratios is due to both the parameter cancelling effect and correlation.

Temperature-dependent rotationally inelastic collisions of OH− and He

We have studied the fundamental rotational relaxation and excitation collision of OH- J=0 <-> 1 with helium at different collision energies. Using state-selected photodetachment in a cryogenic ion trap, the collisional excitation of the first excited rotational state of OH- has been investigated and absolute inelastic collision rate coefficients have been extracted for collision temperatures between 20 and 35 K. The rates are compared with accurate quantum scattering calculations for three different potential energy surfaces. Good agreement is found within the experimental accuracy, but the experimental trend of increasing collision rates with temperature is only in part reflected in the calculations.

Absolute rate coefficients for dielectronic recombination of Na-like Kr25+

The absolute rate coefficients for dielectronic recombination (DR) of sodiumlike krypton ions were measured by employing the electron-ion merged-beam technique at the heavy-ion storage ring CSRm at the Institute of Modern Physics in Lanzhou, China. The measured DR spectrum covers the electron-ion collision energy range of 0--70 eV, encompassing all of the DR resonances due to $3s\ensuremath{\rightarrow}3p$ and part of the DR resonances from $3s\ensuremath{\rightarrow}3d(\mathrm{\ensuremath{\Delta}}n=0)$ and $3s\ensuremath{\rightarrow}4l(\mathrm{\ensuremath{\Delta}}n=1)$ core excitations. A series of peaks associated with DR processes have been identified by the Rydberg formula. The experimental DR results are compared with the theoretical calculations using a relativistic configuration interaction flexible atomic code and the distorted-wave collision package autostructure. A very good agreement has been achieved between the experimental results and the theoretical calculations by considering the strong mixing among the low-energy resonances in both calculations. The experimentally derived DR spectrum is then convolved with a Maxwellian-Boltzmann distribution to obtain the temperature dependent plasma recombination rate coefficients and compared with previously available results from the literature. The present experimental result yields a precise plasma rate coefficients at the low temperature range up to $\ensuremath{\sim}1\ifmmode\times\else\texttimes\fi{}{10}^{6}\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ and the calculated data by Altun et al. [Z. Altun, A. Yumak, N. R. Badnell, S. D. Loch, and M. S. Pindzola, Astron. Astrophys. 447, 1165 (2006)] provide reliable plasma rate coefficients at high temperature range above $2\ifmmode\times\else\texttimes\fi{}{10}^{6}\phantom{\rule{0.16em}{0ex}}\mathrm{K}$.

On the redox reactions between allyl radicals and NOx

NOx mitigation is a central focus of combustion technologies with increasingly stringent emission regulations. NOx can also enhance the autoignition of hydrocarbon fuels and can promote soot oxidation. The reaction between allyl radical (C3H5) and NOx plays an important role in the oxidation kinetics of propene. In this work, we measured the absolute rate coefficients for the redox reaction between C3H5 and NOx over the temperature range of 1000–1252 K and pressure range of 1.5–5.0 bar using a shock tube and UV laser absorption technique. We produced C3H5 by shock heating of C3H5I behind reflected shock waves. Using a Ti:Sapphire laser system with frequency quadrupling, we monitored the kinetics of C3H5 at 220 nm. Unlike low-temperature chemistry, the two target reactions, C3H5 + NO → products (R1) and C3H5 + NO2 → products (R2), exhibited a strong positive temperature dependence for this radical-radical type reaction. However, these reactions did not show any pressure dependence over the pressure range of 1.5–5.0 bar, indicating that the measured rate coefficients are close to the high-pressure limit. The measured values of the rate coefficients resulted in the following Arrhenius expressions (in unit of cm3/molecule/s):k1(C3H5+NO)=1.49×10−10exp(−6083.6KT)(1017−1252K)k2(C3H5+NO2)=1.71×10−10exp(−3675.7KT)(1062−1250K)To our knowledge, these are the first high-temperature measurements of allyl + NOx reactions. The reported data will be highly useful in understanding the interaction of NOx with resonantly stabilized radicals as well as the mutual sensitization effect of NOx on hydrocarbon fuels.

Electron-ion recombination rate coefficients of carbon-like Ar12+

Electron-ion recombination of carbon-like Ar12+ forming Ar11+ has been investigated for the first time by using the cooler storage ring CSRm at the Institute of Modern Physics in Lanzhou, China. The absolute recombination rate coefficients are derived from the measurement in the electron-ion collision energy range of 0–50 eV, covering dielectronic recombination (DR) resonances associated with 2s22p2 and 2s2p3 (Δn = 0) core excitations. Theoretical results are obtained by employing FAC code and compared with the experimental recombination spectrum. An overall agreement is found in resonance energy positions between merged-beam and calculated spectra. Temperature dependent rate coefficients are derived from the measured DR spectrum by convoluting it with a Maxwell–Boltzmann energy distribution and compared with the calculations from the literature. In the presented temperature range 103–107 K, the experimentally derived rate coefficients agree with the theoretical results of Gu (2003 Astrophys. J. 590 1131) within the experimental uncertainties. The calculation by Zatsarinny et al (2004 Astron. Astrophys. 417 1173) underestimates the rate coefficients in the temperature range 103–5 × 104 K. The combination of the experimental results and theoretical calculation provides a benckmark for Ar12+ recombination data used in astrophysical modeling.

Global uncertainty analysis for the RRKM/master equation modeling of a typical multi-well and multi-channel reaction system

Theoretically predicted rate coefficient parameters play an increasing role in combustion kinetic models. Understanding the uncertainty propagation during RRKM/master equation modeling and quantitatively evaluating the uncertainties of the phenomenological rate coefficients would be a great boon to chemical modeling. In the present work, the global uncertainty and sensitivity analysis were performed for a prototypical multiwell and multichannel reaction system (on the C4H7 potential energy surface) over the temperature and pressure range of 300–2300 K and 0.01–100 atm. Six reactions including chemical activation reactions and unimolecular reactions were studied, focusing on the uncertainty of both absolute rate coefficients and their branching ratios. To reveal the nature of uncertainty propagation from input parameters at different theoretical levels, five scenarios were designed to mimic the uncertainty from high-, moderate- and low- levels of theories. For absolute rate coefficients, the temperature dependence of uncertainties for all the reactions is found to be much stronger than the pressure dependence. The pressure dependence is mainly determined by the reaction type (chemical activation or thermal dissociation, directly-connected or well-skipping). For the branching ratio, sensitivity analysis shows that the input parameters that are very important in determining the absolute rate coefficients do not necessarily have high sensitivity coefficients in predicting the branching ratio. As a consequence, the uncertainty of the theoretically calculated branching ratio can be smaller than that of the rate coefficients.

Enhancement of electron–ion recombination rates at low energy range in the heavy ion storage ring CSRm**Project supported by the National Key Research and Development Program of China (Grant No. 2017YFA0402300) and the National Natural Science Foundation of China (Grant Nos. U1932207, 11904371, and U1732133).

Recombination of Ar14+, Ar15+, Ca16+, and Ni19+ ions with electrons has been investigated at low energy range based on the merged-beam method at the main cooler storage ring CSRm in the Institute of Modern Physics, Lanzhou, China. For each ion, the absolute recombination rate coefficients have been measured with electron–ion collision energies from 0 meV to 1000 meV which include the radiative recombination (RR) and also dielectronic recombination (DR) processes. In order to interpret the measured results, RR cross sections were obtained from a modified version of the semi-classical Bethe and Salpeter formula for hydrogenic ions. DR cross sections were calculated by a relativistic configuration interaction method using the flexible atomic code (FAC) and AUTOSTRUCTURE code in this energy range. The calculated RR + DR rate coefficients show a good agreement with the measured value at the collision energy above 100 meV. However, large discrepancies have been found at low energy range especially below 10 meV, and the experimental results show a strong enhancement relative to the theoretical RR rate coefficients. For the electron–ion collision energy below 1 meV, it was found that the experimentally observed recombination rates are higher than the theoretically predicted and fitted rates by a factor of 1.5 to 3.9. The strong dependence of RR rate coefficient enhancement on the charge state of the ions has been found with the scaling rule of q3.0, reproducing the low-energy recombination enhancement effects found in other previous experiments.

Investigation of the Absorption Cross Section of Phenyl Radical and Its Kinetics with Methanol in the Gas Phase Using Cavity Ring-Down Spectroscopy and Theoretical Methodologies.

Cavity ring-down spectroscopy (CRDS) was used to measure the absorption cross section of phenyl radicals (C6H5•) at 504.8 nm (2B1 ← 2A1 transition) in the nitrogen atmosphere at 40 Torr total pressure and 298 K using nitrosobenzene (C6H5NO) as the radical precursor. At 504.8 nm, the absorption cross section was measured to be σphenyl504.8nm = (5.7 ± 1.4) × 10-19 cm2 molecule-1. The absorption cross section was independent of the total pressure range (40-200 Torr) over which it was studied with a precursor concentration of (4-5) × 1013 molecules cm-3. In addition to this, the absolute rate coefficients for the reaction of phenyl radicals with methanol were measured over the temperature range of 263-298 K and at 40 Torr pressure with N2 using CRDS. The temperature-dependent rate coefficient for the title reaction over the studied temperature range was obtained to be k263-298Kexperiment (T) = (1.38 ± 0.60) × 10-11 exp [-(1764 ± 321)/T] cm3 molecule-1 s-1 with a rate coefficient of k(T) = (3.50 ± 0.32) × 10-14 cm3 molecule-1 s-1 at 298 K. The effect of pressure and laser fluence was found to be negligible within the experimental uncertainties in the studied range. In addition, to complement our experimental findings, the T-dependent rate coefficients for the title reaction were investigated using computational methods. The B3LYP/6-311 + G(d,p) level of theory was used in combination with canonical variational transition-state theory with small-curvature tunneling to calculate the rate coefficients. The T-dependent rate coefficient in the range of 200-400 K was obtained as k200-400Ktheory (T) = 2.43 × 10-13 exp[-(478.38/T)] cm3 molecule-1 s-1 with a room-temperature (298 K) rate coefficient of 4.67 × 10-14 cm3 molecule-1 s-1.