Direct ab initio dynamics study of the OH + HOCO reaction

The reaction between OH and HOCO has been examined using the coupled-cluster method to locate and optimize the critical points on the ground-state potential energy surface. The energetics are refined using the coupled-cluster method with basis set extrapolation to the complete basis set (CBS) limit. Results show that the OH + HOCO reaction produces H2O + CO2 as final products and the reaction passes through an HOC(O)OH intermediate. In addition, the OH + HOCO reaction has been studied using a direct dynamics method with a dual-level ab initio theory. Dynamics calculations show that hydrogen bonding plays an important role during the initial stages of the reaction. The thermal rate constant is estimated over the temperature range 250-800 K. The OH + HOCO reaction is found to be nearly temperature-independent at lower temperatures, and at 300 K, the thermal rate constant is predicted to be 1.03 x 10(-11) cm3 molecule(-1) s(-1). In addition, there may be an indication of a small peak in the rate constant at a temperature between 300 and 400 K.     

Ab initio study of the potential energy surface for the OH+CO-->H+CO2 reaction

Potential energy surface for the reaction OH+CO-->H+CO2 has been calculated using the complete active space self-consistent-field and multireference configuration interaction methods with the correlation consistent triple-, quadruple-, and quintuple-zeta basis sets. A specific- reaction-parameters density functional theory has been suggested, in which the B3LYP functional is reoptimized to give the highly accurate potential energy surface with less computational efforts.     

The mechanism of the OH + CO reaction and the stability of the HOCO radical

The mechanism of the reaction between OH radicals and CO is discussed in relation to recent experiments which indicate that the rate constant, k = ?(dln[OH]/dt)/[CO], depends on total pressure. It is shown that this observation is quite consistent with the known spectroscopic and thermodynamic properties of the HOCO radical, as long as the dissociation of HOCO to H + CO₂ is no faster than that to OH + CO.     

Analysis of the H + D2 reaction mechanism through consideration of the intrinsic reactant polarisation

The effect of reactant polarisation on the dynamics of the title reaction at collision energies up to 1.6 eV is analysed in depth. The analysis takes advantage of two novel theoretical concepts: intrinsic reaction properties and stereodynamical portraits. Exact quantum methods are used to determine the polarisation moments that quantify the intrinsic reactant polarisation at various levels of detail, including or not product state and/or scattering angle resolution. The data is then examined with the aid of stereodynamical portraits, which facilitate the rationalisation of the stereochemical effects that are relevant for the reaction dynamics. This allows for detailed characterisations of the so-called direct and delayed reaction mechanisms.     

Kinetic study of the OH + ethylene reaction using frequency-modulated laser absorption spectroscopy

The pressure dependence of the OH + C₂H₄ addition reaction has been investigated using frequency-modulated laser absorption spectroscopy to monitor OH kinetics. Bimolecular rate coefficients for the title reaction are reported in argon bath gas at room temperature and total pressures ranging from 2 to 361 Torr. The pressure-dependent rate coefficients measured here agree well with the majority of published kinetic studies under similar conditions. Previous high-level ab initio calculations have identified a prereaction complex on the OH + C₂H₄ potential energy surface. The influence of this complex on the OH + C₂H₄ kinetics has been investigated using one-dimensional master equation analyses of the current and previous experimental measurements.     

State-to-state dynamics of the Cl + CH3OH --> HCl + CH2OH reaction

Molecular chlorine, methanol, and helium are co-expanded into a vacuum chamber using a custom designed "late-mixing" nozzle. The title reaction is initiated by photolysis of Cl2 at 355 nm, which generates monoenergetic Cl atoms that react with CH3OH at a collision energy of 1960 +/- 170 cm(-1) (0.24 +/- 0.02 eV). Rovibrational state distributions of the nascent HCl products are obtained via 2 + 1 resonance enhanced multiphoton ionization, center-of-mass scattering distributions are measured by the core-extraction technique, and the average internal energy of the CH3OH co-products is deduced by measuring the spatial anisotropy of the HCl products. The majority (84 +/- 7%) of the HCl reaction products are formed in HCl(v = 0) with an average rotational energy of [Erot] = 390 +/- 70 cm(-1). The remaining 16 +/- 7% are formed in HCl(v = 1) and have an average rotational energy of [Erot] = 190 +/- 30 cm(-1). The HCl(v = 1) products are primarily forward scattered, and they are formed in coincidence with CH2OH products that have little internal energy. In contrast, the HCl(v = 0) products are formed in coincidence with CH2OH products that have significant internal energy. These results indicate that two or more different mechanisms are responsible for the dynamics in the Cl + CH3OH reaction. We suggest that (1) the HCl(v = 1) products are formed primarily from collisions at high impact parameter via a stripping mechanism in which the CH2OH co-products act as spectators, and (2) the HCl(v = 0) products are formed from collisions over a wide range of impact parameters, resulting in both a stripping mechanism and a rebound mechanism in which the CH2OH co-products are active participants. In all cases, the reaction of fast Cl atoms with CH3OH is with the hydrogen atoms on the methyl group, not the hydrogen on the hydroxyl group.     

The OH(v = 9) + O3 reaction pathway

The oxygen-hydrogen system, including the reactive species H, O, H₂, O₂, O₃, OH, and HO₂, is very complex, and contains numerous reactions whose kinetics and branches have been insufficiently explored. In the present study we use computer modeling to simulate observations made in a 300-K ozone-hydrogen mixture, in which a critical H₂ pressure leads to rapid ozone decomposition, and generation of high concentrations of atomic oxygen. Initiation of the reaction chain involves heterogeneous O and/or H atom production, and the chain branching step is the reaction OH(v) + O₃ → OH + O + O₂, which is shown to be the predominant pathway for these reactants. The critical H₂ pressure (ca. 3 torr) sets important constraints upon the system kinetics.     

A shock tube study of the OH + OH → H2O + O reaction

The rate coefficient for the reaction has been determined in mixtures of nitric acid (HNO₃) and argon in incident shock wave experiments. Quantitative OH time-histories were obtained by cw narrow-linewidth uv laser absorption of the R₁(5) line of the A² σ⁺ ← X² Π_i (0,0) transition at 32606.56 cm^?1 (vacuum). The experiments were conducted over the temperature range 1050–2380 K and the pressure range 0.18–0.60 atm. The second-order rate coefficient was determined to be with overall uncertainties of +11%, ?16% at high temperatures and +25%, ?22% at low temperatures. By incorporating data from previous investigations in the temperature range 298–578 K, the following expression is determined for the temperature range 298–2380 K © 1994 John Wiley & Sons, Inc.     

Kinetics of the OH + HCNO reaction

The kinetics of the OH + HCNO reaction was studied. The total rate constant was measured by LIF detection of OH using two different OH precursors, both of which gave identical results. We obtain k = (2.69 +/- 0.41) x 10(-12) exp[(750.2 +/- 49.8)/T] cm(3) molecule(-1) s(-1) over the temperature range 298-386 K, with a value of k = (3.39 +/- 0.3) x 10(-11) cm(3) molecule(-1) s(-1) at 296 K. CO, H(2)CO, NO, and HNO products were detected using infrared laser absorption spectroscopy. On the basis of these measurements, we conclude that CO + H(2)NO and HNO + HCO are the major product channels, with a minor contribution from H(2)CO + NO.     

IR kinetic spectroscopy investigation of the CH4 + O(1D) reaction

The branching of the title reaction into several product channels has been investigated quantitatively by laser infrared kinetic spectroscopy for CH(4) and CD(4). It is found that OH (OD) is produced in 67 +/- 5% (60 +/- 5%) yield compared to the initial O((1)D) concentration. H (D) product is produced in 30 +/- 10%(35 +/- 10%). H(2)CO is produced in 5% yield in the CH(4) system (it was not possible to measure the CD(2)O yield in the CD(4) case). D(2)O is produced in 8% yield in the CD(4) system (it was not feasible to measure the H(2)O yield). The ratio of the overall rate constant of the CD(4) reaction to the overall rate constant of the O((1)D) + N(2)O reaction was determined to be 1.2(5) +/- 0.1. A measurement of the reaction of O((1)D) with NO(2) gave 1.3 x 10(-10) cm(3) molecule(-1) s(-1) relative to the literature values for the rate constants of O((1)D) with H(2) and CH(4). Hot atom effects in O((1)D) reactions were observed.     

Theoretical rate coefficients for the exchange reaction OH + D--> OD + H

In this work quasiclassical trajectory calculations were carried out to determine directly the rate coefficients for the isotopic exchange reaction, OH + D-->OD + H, using a potential-energy surface that carefully accounts for the long-range interactions. The calculated thermal rate coefficients are in good agreement with the experimental results.     

Dynamics of the CH3 + OH reaction

We study dynamics of the CH₃ + OH reaction over the temperature range of 300–2500 K using a quasiclassical method for the potential energy composed of explicit forms of short‐range and long‐range interactions. The explicit potential energy used in the study gives minimum energy paths on potential energy surfaces showing barrier heights, channel energies, and van der Waals well, which are consistent with ab initio calculations. Approximately, 20% of CH₃ + OH collisions undergo OH dissociation in a direct‐mode mechanism on a subpicosecond scale (<50 fs) with the rate coefficient as high as ～10^?10 cm³ molecule^?1 s^?1. Less than 10% leads to the formation of excited intermediates CH₃OH? with excess vibrational energies in CO and OH bonds. CH₃OH? stabilizes to CH₃OH, redissociates back to reactants, or forms one of various products after intramolecular energy redistribution via bond dissociation and formation on the time scale of 50–200 fs. The principal product is ¹CH₂ (k being ～10^?11), whereas ks for CH₂OH, CH₂O, and CH₃O are ～10^?12. The minor products are HCOH and CH₄ (k～10^?13). The total rate coefficient for CH₃ + OH → CH₃OH? → products is ～10^?11 and is weakly dependent on temperature. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 455–466, 2011     

Water effect on the OH + HCl reaction

Hydrochloric acid is a major reservoir for chlorine radicals in the atmosphere. Chlorine radicals are chemically reactivated by the relatively slow attack of OH radical on HCl. Through the formation of hydrogen-bonded complexes, water has a dramatic effect on the rate of this reaction. The introduction of water opens several new reaction pathways with rate coefficients that are faster than the "bare" reaction. Accounting for the low fraction of hydrogen bonded water complexes in the atmosphere, the present results suggest that these new mechanisms involving water can contribute, although modestly, to the total chemical reactivation of chlorine from HCl in the lower troposphere. The first reported value for the equilibrium constant for the formation of H(2)O·HCl complex, which is important in understanding the removal of HCl from the atmosphere by deposition, is presented.     

Kinetics study of the OH + alkene --> H2O + alkenyl reaction class

In this paper we report on the kinetics of hydrogen abstraction for the OH + alkene reaction class, using the reaction class transition state theory (RC-TST) combined with the linear energy relationship (LER) and the barrier height grouping (BHG) approaches. Parameters for the RC-TST were derived from theoretical calculations using a set of 15 reactions representing the hydrogen abstractions from the terminal and nonterminal carbon sites of the double bond of alkene compounds. Both the RC-TST/LER, where only reaction energy is needed at either density functional theory BH&HLYP or semiempirical AM1 levels, and RC-TST/BHG, where no additional information is required, are found to be promising methods for predicting rate constants for a large number of reactions in this reaction class. Detailed error analyses show that, when compared to explicit theoretical calculations, the averaged systematic errors in the calculated rate constants using both the RC-TST/LER and RC-TST/BHG methods are less than 25% in the temperature range 300-3000 K. The estimated rate constants using these approaches are in good agreement with available data in the literature.     

Impact of water on the OH + HOCl reaction

The effect of a single water molecule on the OH + HOCl reaction has been investigated. The naked reaction, the reaction without water, has two elementary reaction paths, depending on how the hydroxyl radical approaches the HOCl molecule. In both cases, the reaction begins with the formation of prereactive hydrogen bond complexes before the abstraction of the hydrogen by the hydroxyl radical. When water is added, the products of the reaction do not change, and the reaction becomes quite complex yielding six different reaction paths. Interestingly, a geometrical rearrangement occurs in the prereactive hydrogen bonded region, which prepares the HOCl moiety to react with the hydroxyl radical. The rate constant for the reaction without water is computed to be 2.2 × 10(-13) cm(3) molecule(-1) s(-1) at room temperature, which is in good agreement with experimental values. The reaction between ClOH···H(2)O and OH is estimated to be slower than the naked reaction by 4-5 orders of magnitude. Although, the reaction between ClOH and the H(2)O···HO complex is also predicted to be slower, it is up to 2.2 times faster than the naked reaction at altitudes below 6 km. Another intriguing finding of this work is an interesting three-body interchange reaction that can occur, that is HOCl + HO···H(2)O → HOCl···H(2)O + OH.     

Angular momentum conservation in the O + OH ↔ O2 + H reaction

We have studied the O + OH ↔ O₂ + H reaction on Varandas's DMBE IV potential using a variety of statistical methods, all involving the RRKM assumption for the HO₂* complex. Comparing our results using microcanonical variational transition‐state theory (μVT) with those using microcanonical/fixed‐J variational transition‐state theory (μVT‐J), we find that the effect of angular momentum conservation on the rate coefficient is imperceptible up to a temperature of about 700 K. Above 700 K angular momentum conservation increasingly reduces the rate coefficient, but only by approximately 21% even at 5000 K. Comparing our μVT‐J calculations with the quasi‐classical trajectory (QCT) results of Miller and Garrett [ 1 ], we confirm their conclusion that non‐RRKM dynamics of the HO₂* complex reduces the rate coefficient by about a factor of 2 independent of temperature. Our calculations of k^(c), the rate coefficient for HO₂* formation from O + OH, are in excellent agreement with the QCT results of Miller and Garrett. Although the differences are not large, we find k_CVT^(c) > k_μVT^(c) > k_μVT‐J^(c) > k_QCT^(c), where CVT stands for canonical variational transition‐state theory. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 753–756, 1999     

Energetics and kinetics of the reaction of HOCO with hydrogen atoms

The potential energy surface for the reaction of HOCO radicals with hydrogen atoms has been explored using the CCSD(T)/aug-cc-pVQZ ab initio method. Results show that the reaction occurs via a formic acid (HOC(O)H) intermediate, and produces two types of products: H(2)O+CO and H(2)+CO(2). Reaction enthalpies (0 K) are obtained as -102.0 kcalmol for the H(2)+CO(2) products, and -92.7 kcalmol for H(2)O+CO. Along the reaction pathways, there exists a nearly late transition state for each product channel. However, the transition states locate noticeably below the reactant asymptote. Direct ab initio dynamics calculations are also carried out for studying the kinetics of the H+HOCO reaction. At room temperature, the rate coefficient is predicted to be 1.07x10(-10)cm(3) molec(-1) s(-1) with a negligible activation energy E(a)=0.06 kcalmol, and the branching ratios are estimated to be 0.87 for H(2)+CO(2), and 0.13 for H(2)O+CO. In contrast, the product branching ratios have a strong T dependence. The branching ratio for H(2)O+CO could increase to 0.72 at T=1000 K.     

The rate constant of the reaction HO2 + COCO2 + OH

The high-temperature oxidation of formaldehyde in the presence of carbon monoxide was investigated to determine the rate constant of the reaction HO₂ + CO ? CO₂ + OH (10). In the temperature range of 878–952°K from the initial parts of the kinetic curves of the HO₂ radicals and CO₂ accumulation at small extents of the reaction, when the quantity of the reacted formaldehyde does not exceed 10%, it was determined that the rate constant k₁₀ is A computer program was used to solve the system of differential equations which correspond to the high-temperature oxidation of formaldehyde in the presence of carbon monoxide. The computation confirmed the experimental results. Also discussed are existing experimental data related to the reaction of HO₂ with CO.     

Kinetics of the hydrogen abstraction R−OH + H → R•−OH + H2 reaction class: An application of the reaction class transition state theory

This paper presents an application of the reaction class transition state theory (RC‐TST) to predict thermal rate constants for hydrogen abstraction reactions of the type R‐OH + H → R^?‐OH + H₂. We have derived all parameters for the RC‐TST method with linear energy relationships (LERs) and the barrier height grouping (BHG) approach for this reaction class from rate constants of 37 representative reactions divided in two types of hydrogen abstraction, namely from α carbon sites and non‐α carbon sites two training sets. Error analyses indicate that the RC‐TST/LER, where only reaction energy is needed, and RC‐TST/ BHG, where no other information is needed, can predict rate constants for any reaction in this reaction class with satisfactory accuracy for combustion modeling. Specifically for this reaction class, the RC‐TST/LER and RC‐TST/BHG methods have, respectively, less than 40% and 90% systematic errors in the predicted rate constants, when compared to the explicit full TST/Eckart method. The branching ratio analysis shows that in the low‐temperature regime α abstractions are dominant, whereas, for T > 1500 K, abstractions at other sites become more important. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 43: 78–98, 2011     

Quantum molecular dynamics study of the reaction of O2 with HOCO

The reaction of O2 with HOCO has been studied by using an ab initio direct dynamics method based on the UB3PW91 density functional theory. Results show that the reaction can occur via two mechanisms: direct hydrogen abstraction and an addition reaction through a short-lived HOC(O)O2 intermediate. The lifetime of the intermediate is predicted to be 660 +/- 30 fs. Although it is an activated reaction, the activation energy is only 0.71 kcal/mol. At room temperature, the obtained thermal rate coefficient is 2.1 x 10(-12) cm3 molecule(-1) s(-1), which is in good agreement with the experimental results.