Calculated Rate Coefficients Research Articles

Inelastic Processes in Nickel–Hydrogen Collisions

Abstract The cross sections and rate coefficients for inelastic processes in low-energy collisions of nickel atoms and positive ions with hydrogen atoms and negative ions are calculated for the collisional energy range 10−4–100 eV and for the temperature range 1000–10,000 K. 74 covalent and three ionic states correlated to 11 molecular symmetries are considered. 3380 partial inelastic processes are treated in total. The study of nickel–hydrogen collisions is performed by the quantum model methods within the Born–Oppenheimer formalism. The electronic structure of the collisional quasimolecule is calculated by the semiempirical asymptotic method for each considered molecular symmetry. For nuclear dynamic calculations the simplified method in combination with the Landau–Zener model is used. Nuclear dynamics within each considered symmetry is treated separately, and the total rate coefficients for each inelastic process have been summed over all symmetries. The largest values of the rate coefficients (exceeding 10−8 cm3 s−1) correspond to the mutual neutralization processes in collisions Ni+(3d 9 2 D) + H−(1s 2 1 S) (the ground ionic state being the initial state), as well as in Ni+(3d 84s 4,2 F) + H−(1s 2 1 S) (the first excited and the second excited ionic states being the initial states) collisions. At the temperature of 6000 K, the rate coefficients with large magnitudes have the values from the ranges (1.35−5.87) × 10−8 cm3 s−1 and (1.02−6.77) × 10−8 cm3 s−1, respectively. The calculated rate coefficients with large and moderate values are important for non–local thermodynamic equilibrium stellar atmosphere modeling.

Calculations of electron-impact excitation and dielectronic recombination rate coefficients of highly charged silicon ions

The rate coefficients for dielectronic recombination and electron-impact excitation processes with H-like to Be-like silicon ions (${\mathrm{Si}}^{13+}\text{\ensuremath{-}}{\mathrm{Si}}^{10+}$) are calculated using relativistic distorted-wave approach. The prominent $▵n=1$ and the weaker $▵n=2$ and 3 dielectronic recombination (DR) resonances with $K$-shell excitations are presented, and compared with the existing DR experimental rate coefficients of ${\mathrm{Si}}^{13+}, {\mathrm{Si}}^{12+}$, and ${\mathrm{Si}}^{11+}$ ions, it is found that the theoretical DR rate coefficients are in very good agreement with the experimental results. With the same approach, the direct and resonant electron-impact excitation (EIE) cross sections associated with $1s\ensuremath{-}{n}^{\ensuremath{'}}{l}^{\ensuremath{'}}$ core excitations are calculated for the ground states of ${\mathrm{Si}}^{13+}\text{\ensuremath{-}}{\mathrm{Si}}^{10+}$ ions and found in excellent agreement with the available experiment. Finally, we present the synthesized DR and EIE rate coefficients for the sum of all detected $(13+\ensuremath{\sim}10+)$ charge states of Si and these agree well with the experimental results.

Experimental and chemical kinetic study on the low temperature oxidation of 1,3-butadiene in a jet-stirred reactor

Species concentrations for 1,3-butadiene oxidation were measured in a jet-stirred reactor (JSR) at ϕ = 0.5, 1.0 and 2.0, at 1 atm, in the temperature range of 650 to 1200 K and the residence time of 2 s. AramcoMech 3.0 was modified based on the high-level quantum calculated rate coefficients published, including OH/H/HO2 addition to 1,3-butadiene and subsequent reactions. The modified model was validated against the measured species concentrations in this work and ignition delay times, laminar flame speeds proposed in literatures. Good agreement with experimental data can be observed. In addition, kinetic investigation was carried out. Flux analysis and sensitivity analysis showed that OH/H addition reactions play important roles in determining the reactivity in 1,3-butadiene consumption.

Multipole-moment effects in ion-molecule reactions at low temperatures: part II - charge-quadrupole-interaction-induced suppression of the He+ + N2 reaction at collision energies below kB·10 K.

We report on an experimental and theoretical investigation of the He+ + N2 reaction at collision energies in the range between 0 and kB·10 K. The reaction is studied within the orbit of a highly excited Rydberg electron after merging a beam of He Rydberg atoms (He(n), n is the principal quantum number), with a supersonic beam of ground-state N2 molecules using a surface-electrode Rydberg–Stark decelerator and deflector. The collision energy Ecoll is varied by changing the velocity of the He(n) atoms for a fixed velocity of the N2 beam and the relative yields of the ionic reaction products N+ and N2+ are monitored in a time-of-flight mass spectrometer. We observe a reduction of the total reaction-product yield of ∼30% as Ecoll is reduced from ≈kB·10 K to zero. An adiabatic capture model is used to calculate the rotational-state-dependent interaction potentials experienced by the N2 molecules in the electric field of the He+ ion and the corresponding collision-energy-dependent capture rate coefficients. The total collision-energy-dependent capture rate coefficient is then determined by summing over the contributions of the N2 rotational states populated at the 7.0 K rotational temperature of the supersonic beam. The measured and calculated rate coefficients are in good agreement, which enables us to attribute the observed reduction of the reaction rate at low collision energies to the negative quadrupole moment, Qzz, of the N2 molecules. The effect of the sign of the quadrupole moment is illustrated by calculations of the rotational-state-dependent capture rate coefficients for ion–molecule reactions involving N2 (negative Qzz value) and H2 (positive Qzz value) for |J, M〉 rotational states with J ≤ 5 (M is the quantum number associated with the projection of the rotational angular momentum vector J⃑ on the collision axis). With decreasing value of |M|, J⃑ gradually aligns perpendicularly to the collision axis, leading to increasingly repulsive (attractive) interaction potentials for diatomic molecules with positive (negative) Qzz values and to reaction rate coefficients that decrease (increase) with decreasing collision energies.

Rate constants and molecular recombination pathways of oxygen from quasi-classical trajectory simulations of theO3system

• Investigation of recombination mechanisms using quasi-classical trajectory method. • Direct collisions are more effective for recombination. • Indirect recombinations proceed through orbiting pairs. • Recombination products result in strong non-Boltzmann internal energy distributions. • Recombination products exhibit large vibrational and low rotational quantum numbers. A lack of understanding of the dynamics of molecular recombination has led to the development of a large number of recombination models and methods to quantify recombination rate constants, each with their own set of assumptions and ranges of applicability. This work aims to unravel the complex dynamics behind the recombination of atomic oxygen to molecular oxygen using the quasi-classical trajectory method for the O 3 system. Recombination pathways considered include a single-step “direct” reaction, and a two-step mechanism that involves the formation of a long-lived intermediate which is stabilized through collision with a third body. The latter is further classified as Lindemann or Chaperon recombination pathways depending on the identity of the intermediate and the final product. The classical versions of all three mechanisms are explored in detail for the O 3 system. A time-lag parameter is introduced to quantify the time interval between the intermediate formation and third-body stabilization steps, and the direct collisions are treated as a limiting case when the time lag is zero. It is found that the recombination probabilities reduce as the time-lag is increased. Direct recombination events are dominated by head-on collisions, while the two step recombination events are characterized by a combination of glancing and head-on collisions. The resulting recombination products follow a strongly non-Boltzmann distribution. Recombination rate coefficients are computed through a novel rate coefficient formula that takes into consideration the Poisson distribution in time of third body stabilizing collisions with the orbiting pair characterized by finite lifetimes (on the order of picoseconds) that lead to recombination. Good agreement is obtained with recombination rates computed from detailed balance based on known dissociation rate coefficients. This approach thus enables the direct calculation of recombination rate coefficients at low temperatures, without the need for dissociation rate coefficients and detailed balance.

New theoretical investigation of rotational inelastic (de)-excitation of calcium isocyanide CaNC(2Σ+) in collision with He(1S).

The theoretical study of collisions between atoms and molecules provides a detailed description of the involved mechanisms and greatly contributes to improving atmospheric and astrophysics models. In the present paper, we focus on the new calculation of rate coefficients for the first 25 rotational levels of the CaNC molecule in collision with He. A new 2D potential energy surface (2D-PES), for the CaNC-He system, was determined using the single, double and perturbative triple excitation restricted coupled-cluster method [rccsd(t)] and the standard aug-cc-pVQZ basis sets. This PES presents a global minimum with a well depth of -21.93 cm-1 located at R = 8a0 and γ = 116°. State-to-state collisional excitation cross-sections of the fine-structure levels of CaNC(2Σ+)-He are calculated for energies up to 305 cm-1, which yield, after thermal averaging, rate coefficients up to 70 K. A ΔJ = ΔN propensity rule was observed. A comparison of the CaNC rates with those of valence isoelectronic MgNC has been investigated. These new data are necessary for the CaNC abundance determination and interpretation of its observed lines.

Validating experiments for the reaction H2 + NH2- by dynamical calculations on an accurate full-dimensional potential energy surface.

Ion-molecule reactions play key roles in the field of ion related chemistry. As a prototypical multi-channel ion-molecule reaction, the reaction H2 + NH2- → NH3 + H- has been studied for decades. In this work, we develop a new globally accurate potential energy surface (PES) for the title system based on hundreds of thousands of sampled points over a wide dynamically relevant region that covers long-range interacting configuration space. The permutational invariant polynomial-neural network (PIP-NN) method is used for fitting and the resulting total root mean squared error (RMSE) is extremely small, 0.026 kcal mol-1. Extensive dynamical and kinetic calculations are carried out on this PIP-NN PES. Impressively, a unique phenomenon of significant reactivity suppression by exciting the rotational mode of H2 is reported, supported by both the quasi-classical trajectory (QCT) and quantum dynamics (QD) calculations. Further analysis uncovers that exciting the H2 rotational mode would prevent the formation of the reactant complex and thus suppress the reactivity. The calculated rate coefficients for H2/D2 + NH2- agree well with the experimental results, which show an inverse temperature dependence from 50 to 300 K, consistent with the capture nature of this barrierless reaction. The significant kinetic isotope effect observed by experiments is well reproduced by the QCT computations as well.

Effect of a single water molecule on ˙CH2OH + 3O2 reaction under atmospheric and combustion conditions.

The hydroxymethyl (˙CH2OH) radical is an important intermediate species in both atmosphere and combustion reaction systems. The rate coefficients for ˙CH2OH + 3O2 and (˙CH2OH + 3O2 (+H2O)) reactions were calculated using the Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation (ME) simulation and canonical variational transition state theory (CVT) between the temperature range of 200 to 1500 K based on the potential energy surface constructed using CCSD(T)//ωB97XD/6-311++G(3df,3pd). The results show that ˙CH2OH + 3O2 leads to the formation of CH2O and HO2 at temperatures below 800 K, and goes back to reactants at high temperature (>1000 K). When a water molecule is added to the reaction, the formation of CH2O and HO2 is favored at all temperatures. The calculated rate coefficient for the ˙CH2OH + 3O2 (2.8 × 10-11 cm3 molecule-1 s-1 at 298 K) is in good agreement with the previous experimental values (∼1 × 10-11 cm3 molecule-1 s-1 at 298 K). The rate coefficients for the water-assisted reaction (2.4 × 10-16 cm3 molecule-1 s-1 at 1000 K) is at least 3-4 orders of magnitude smaller than the water-free reaction (6.2 × 10-12 cm3 molecule-1 s-1 at 1000 K). This result is consistent with the similar types of reaction system. Our calculations also predict that the effect of a single water molecule favors the formation of CH2O in the combustion condition. However, the water-free reaction favors the formation of CH2O in the atmospheric condition. The current study helps to understand how a single water molecule changes the reaction mechanism and chemical kinetic behaviour under atmospheric and combustion conditions.

Kinetic and dynamic studies of the NH2+ + H2 reaction on a high-level ab initio potential energy surface.

Gas-phase ion-molecule reactions have attracted considerable attention due to their importance in the fields of interstellar chemistry, plasma chemistry, and combustion chemistry. The reaction of an amino radical cation with a hydrogen molecule is one of the crucial steps in the gas-phase formation of ammonia in the interstellar medium (ISM). The dynamics and kinetics of the NH2+ + H2 reaction are studied using the quasi-classical trajectory approach on a newly constructed ab initio potential energy surface (PES) for the ground electronic state. The PES is fitted by the fundamental invariant-neural network method, resulting in a total root mean square error (RMSE) of 0.061 kcal mol-1. Dynamics calculations show that, on one hand, the vibrational excitation of H2 largely promotes the reaction. On the other hand, the fundamental excitation of each vibrational mode of NH2+ inhibits the reaction at low collision energies which has a negligible effect at high collision energies except for the symmetric stretching mode. The relatively higher efficacy of the symmetric stretching mode than that of the asymmetric stretching mode can be rationalized by the underlying reaction mechanisms. In addition, the calculated rate coefficients of the reaction agree reasonably well with the available experimental results.

Theoretical studies of the reactions of methyl radical with dimethyl ether and 1,2-ethanediol

The CH3OCH3 + CH3 and (CH2OH)2 + CH3 reactions were characterized using CCSD(T)/CBS//M06-2x/cc-pVTZ theory. For the two reactions, a total of five reaction channels have been described, including the H-abstraction channels. The rate coefficients were calculated by CVT/SCT and the fitting parameters of Arrhensive formulas were given. The calculated rate coefficients agreed well with the available reference values. Note that the H-abstraction channel is the dominant channel over almost the calculated temperature range for the CH3OCH3 + CH3 reaction. The H-abstraction from CH2 group is predominant less than 1100 K and the the H-abstraction from the OH group become important higher than 1200 K in the (CH2OH)2 + CH3 reaction.

Theoretical study on isomerization, decomposition and ring-closure reaction kinetics of methyl pentanoate radicals

A comprehensive study on the isomerization, decomposition and ring-closure reaction kinetics, as well as thermodynamic properties of methyl pentanoate radicals were carried out in this work. The M06–2X/cc-pVTZ level of theory was employed to optimize geometries and analyze frequencies for all the stationary points on the potential energy surfaces. The CCSD(T) method with two basis sets, cc-pVDZ and cc-pVTZ, was used to calculate single point energies, which were further extrapolated to the complete basis set (CBS) limit to construct the potential energy surfaces. The energy calculation results indicated that isomerization of δ-R to α-R, decomposition of γ-R to CH2C(=O)OCH3 and propene, and ring-closure reaction of δ-R to 1-methoxycyclopentanoxyl radical are the most energetically favored reactions among the studied isomerization, decomposition and ring-closure reaction channels, respectively. High pressure limit, and temperature and pressure dependent rate coefficients were determined by solving the one-dimensional energy-dependent master equations with Tsinghua University Minnesota Master Equation program (TUMME). The rate coefficients and branching ratios were found to be significantly affected by temperature and pressure. The decomposition reactions yielding small unsaturated esters or small ester radicals dominate at high temperatures, while the isomerization reactions proceeding via five- and six-membered ring saddle points, as well as the ring-closure reactions play more important roles at low temperatures. Significant discrepancies are observed between the theoretically calculated rate coefficients and estimated results. The thermochemical properties of methyl pentanoate radicals were calculated using isodesmic reaction method and atomization method together with the multistructural torsional anharmonicity partition functions. This study provides accurate kinetic and thermodynamic data on methyl pentanoate radicals, which are expected to advance our understanding of combustion chemistry of methyl pentanoate and larger methyl esters.

Reaction of •OH with CHCl=CH-CHF2 and its atmospheric implication for future environmental-friendly refrigerant

Abstract In order to understand the atmospheric implication of the chlorinated hydrofluoroolefin (HFO), the geometrical structures and the IR absorption cross sections of the stereoisomers 1-chloro-3,3-difluoropropene were studied using the B3LYP/6-31G(3df) and M06-2X/6-31G(3df) methods in the gas phase. The cis-trans isomerization was assessed using the M06-2X/6-311++G(3df,p)//6-31+G(3df,p) method. The latter method was also employed for thermochemistry and the rate coefficients of the reactions of •OH with the cis- and trans-isomers in the temperature ranging from 200 to 400 K. The computational method CCSD/cc-pVTZ//M06-2X/6-31+G(3df,p) was used to benchmark the rate coefficients. It turns out that, the trans-isomer is more stable than cis-isomer and the trans- to cis-isomerization is thermodynamically unfavorable. The rate coefficient follows the Gaussian law with respect to the inverse of temperature. At the global temperature of stratosphere, the calculated rate coefficients served to estimate the atmospheric lifetime along with the photochemical ozone creation potential (POCP). This yielded lifetimes of 4.31 and 7.31 days and POCPs of 3.80 and 2.23 for the cis- and trans-isomer, respectively. The radiative forcing efficiencies gave 0.0082 and 0.0152 W m−2 ppb−1 for the cis- and trans-isomer, respectively. The global warming potential approached zero for both stereoisomers at 20, 100, and 500 years time horizons.

Rotational excitation of H3O+ cations by para-H2: improved collisional data at low temperatures

ABSTRACT The hydronium cation plays a crucial role in interstellar oxygen and water chemistry. While its spectroscopy was extensively investigated earlier, the collisional excitation of H3O+ is not well studied yet. In this work, we present state-to-state collisional data for the rotational de-excitation of both ortho- and para-H3O+ due to para-H2 impact. The cross sections are calculated within the close-coupling formalism using our recent, highly accurate, rigid-rotor potential energy surface for this collision system. The corresponding thermal rate coefficients are computed up to 100 K. For para-H3O+, the lowest 20 rotation-inversion states were considered in the calculations, while for ortho-H3O+, the lowest 11 states are involved (up to j ≤ 5), so all levels with rotational energy below 420 K (292 cm−1) are studied. In order to analyse the impact of the new collisional rate coefficients on the excitation of H3O+ in astrophysical environments, radiative transfer calculations are also provided. The most relevant emission lines from an astrophysical point of view are studied, taking into account the transitions at 307, 365, 389, and 396 GHz. We show that our new collisional data have a non-negligible impact (from a few per cents up to about a factor of 3) on the brightness and excitation temperatures of H3O+, justifying the revision of the physical conditions in the appropriate astrophysical observations. The calculated rate coefficients allow one to recalculate the column density of hydronium in interstellar clouds, which can lead to a better understanding of interstellar water and oxygen chemistry.

SiS Formation in the Interstellar Medium through Si+SH Gas-phase Reactions

Abstract Silicon monosulfide is an important silicon-bearing molecule detected in circumstellar envelopes and star-forming regions. Its formation and destruction routes are not well understood, partially due to the lack of detailed knowledge on the involved reactions and their rate coefficients. In this work we have calculated and modeled the potential energy surface (PES) of the HSiS system employing highly accurate multireference electronic structure methods. After obtaining an accurate analytic representation of the PES, which includes long-range energy terms in a realistic way via the DMBE method, we have calculated rate coefficients for the Si+SH → SiS+H reaction over the temperature range of 25–1000 K. This reaction is predicted to be fast, with a rate coefficient of ∼1 × 10−10 cm3 s−1 at 200 K, which substantially increases for lower temperatures (the temperature dependence can be described by a modified Arrhenius equation with α = 0.770 × 10−10 cm3 s−1, β = −0.756, and γ = 9.873 K). An astrochemical gas-grain model of a shock region similar to L1157-B1 shows that the inclusion of the Si+SH reaction increases the SiS gas-phase abundance relative to H2 from 5 × 10−10 to 1.4 × 10−8, which perfectly matches the observed abundance of ∼2 × 10−8.

A Combined Experimental and Theoretical Study to Determine the Kinetics of 2-Ethoxy Ethanol with OH Radical in the Gas Phase.

The reactivity of 2-ethoxy ethanol with OH radicals was experimentally measured in the temperature range of 278-363 K using the pulsed laser photolysis-laser-induced fluorescence (PLP-LIF) technique. The rate coefficient at room temperature was measured to be (1.14 ± 0.03) × 10-11 cm3 molecule-1 s-1, and the Arrhenius expression was derived to be kexpt278-363K = (1.61 ± 0.35) × 10-13 exp{(1256 ± 236)/T} cm3 molecule-1 s-1. Computational calculations were performed to compute the kinetics of the titled reaction in the temperature range of 200-400 K using advanced methods incorporated with tunneling correction at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-31+G(d,p) level of theory. The Arrhenius expression derived from the computationally calculated rate coefficients is ktheo200-400K = (1.59 ± 0.35) × 10-13exp{(1389 ± 62)/T} cm3 molecule-1 s-1. The feasibility of each reaction pathway was also determined using the calculated thermochemical parameters. Atmospheric implication parameters such as cumulative atmospheric lifetime and photochemical ozone creation potential were calculated and are discussed in this paper.

Comprehensive Chemistry of HeH+ in the Early Universe*

Abstract The recent detection of the helium hydride ion (HeH+) in the planetary nebula NGC 7027 has inspired studies revisiting the dominant processes for its formation and destruction. Because radiative association is the primary formation mechanism for the helium hydride ion at all redshifts, and many early universe chemistry models rely on accurate results for calculations of destruction rates, we explicitly computed rovibrationally distinguished partial cross sections and rate coefficients of helium hydride formation via radiative association, and modeled the abundance of HeH+ in the early universe using recently available rate coefficients for all relevant formation and destruction reactions. The rate coefficients for the radiative association formation reaction of HeH+ and radiative charge transfer in He+ + H collisions were obtained using two distinct methods. Our newly calculated rate coefficients along with other recently reported He chemistry reactions and updated cosmological parameters were incorporated into a new calculation of the abundance of HeH+ for redshifts between z = 10 and 4000. We find that the abundance of the helium hydride ion is at least three orders of magnitude larger than previous predictions for redshifts near z = 20. Rovibrationally distinguished radiative association rate coefficients are given as a function of temperature, and the significance of stimulated radiative association for redshifts z > 400 is also shown.

Kinetics of chemical processes: From molecular to industrial scale

Combining spectroscopic and transient kinetic techniques provides access to the identification and quantification of active sites and corresponding turnover frequencies of catalyzed reactions [1]. Ab initio calculated rate coefficients combined with network generation codes allow so-called microkinetic models accounting for all relevant elementary steps of complex reaction networks. Computational Fluid Dynamics (CFD) account for the scale-dependent transport of mass, energy and momentum and, hence, renders the design of an industrial process based on the intrinsic chemical kinetics possible. These theoretical and experimental achievements cannot be a substitute for the insights provided by the analysis of a catalytic cycle in terms of a limited number of kinetically significant steps [2]. We analyse the kinetics of a single-path reaction represented as a closed sequence of two steps [3]. We discuss some examples of chemical looping processes providing, in contrast to catalytic technology, the possibility to perform the steps of a closed sequence at different conditions.

Effect of Initiator Structure on Thiol‐Ene Polymerization: A DFT Study

AbstractThe performance of commercial initiators on thiol‐ene polymerization has been investigated by utilizing the M062X/6‐31++G(d,p) level of theory. The reactivity of initiators has been explained by the rate coefficients of addition (ki), which is considered side reaction and hydrogen abstraction (kHA) reactions. In this respect, radicals generated from azobisisobutyronitrile (AIBN) and 2,2‐dimethoxy‐2‐phenylacetophenone (DMPA) have been modeled. In the case of AIBN and the propene‐methyl thiol couple as reactants, it has been illustrated that side reaction is highly possible because the calculated rate coefficients ki and kHA are close to each other 1.02E+00 and 1.50E+02 l mol–1 s–1, respectively. In styrene, methyl methacrylate, and maleimide applications, the discrepancy between these reaction rates is relatively less. The high reactivity of DMPA has been explained by possessing high kHA values of formed radicals. The hydrogen abstraction reaction is significantly faster than the addition reactions for generated radicals methyl (CH3•) and benzoyl (C6H5CO•). For methyl methacrylate, side reaction is probable even in the application of DMPA since relatively fast addition reactions (the ki for CH3• and C6H5CO• radicals are 4.71E+04 and 3.42E+04 l mol–1 s–1 respectively.). Styrene and maleimide show a similar reactivity tendency with methyl methacrylate.

Kinetics of the Reactions of Ozone with Halogen Atoms in the Stratosphere

It is well established that reaction cycles involving inorganic halogens contribute to the depletion of ozone in the atmosphere. Here, the kinetics of O3 with halogen atoms (Cl, Br, and I) were investigated between 180 and 400 K, expanding the temperature range relative to prior studies. Canonical variational transition state theory including small curvature tunneling correction (CVT/SCT) were considered, following the construction of the potential energy surfaces. MRCI + Q/aug-ano-pVTZ//MP2/aug-cc-pV(T + d)Z and MRCI + Q/aug-ano-RCC-VTZP//MP2/aug-cc-pV(T + d)Z levels of theory were used to calculate the kinetic parameters. Calculated rate coefficients were used to fit the Arrhenius equations, which are obtained to be k1 = (3.48 ± 0.4) × 10−11 exp[(−301 ± 64)/T] cm3 molecule−1 s−1, k2 = (3.54 ± 0.2) × 10−11 exp[(−990 ± 35)/T] cm3 molecule−1 s−1 and k3 = (1.47 ± 0.1) × 10−11 exp[(−720 ± 42)/T] cm3 molecule−1 s−1 for the reactions of O3 with Cl, Br, and I atoms, respectively. The obtained rate coefficients for the reactions of O3 with halogen atoms using CVT/SCT are compared to the latest recommended rate coefficients by the NASA/JPL and IUPAC evaluations. The reactivity trends and pathways of these reactions are discussed.

Radiative association of atomic and ionic nitrogen

ABSTRACT Radiative association for the formation of molecular nitrogen cation ${\rm{N}}_2^ + $ during the collision of an N(4Su) atom and an N+(3Pg) ion is investigated. The corresponding cross-sections and rate coefficients are computed by the quantum mechanical method based on ab initio potential energy curves and transition dipole moments, which are obtained by the internally contracted multireference configuration interaction method with the Davidson correction and aug-cc-pCV5Z-DK basis set. A number of low-lying doublet, quartet, and sextet states correlating to the N(4Su) + N+(3Pg) dissociation limit are considered. Hence, we investigate a number of dipole-allowed transitions and determine their contributions to the radiative association. The results show that transitions originating in the f4Πu, D2Πg, ${{\rm{B}}^2}\Sigma _{\rm{u}}^ + $, ${{\rm{1}}^4}\Sigma _{\rm{g}}^{\rm{ + }}$, and ${{\rm{1}}^6}\Sigma _{\rm{u}}^{\rm{ + }}$states are the main contributors for the radiative association process. The calculated rate coefficients are valid for temperatures from 100 to 10 000 K and fitted to the analytical function suitable for astrochemical reaction applications.