Absolute rate constants, reactive cross-sections and isotopic branching ratio for the reaction of O(1D) with HD

Thomas, L.; Naik, Prakash D.; Volpp, Hans-Robert; Wolfrum, J.; Arusi-Parpar, Talya; Bar, Ilana; Rosenwaks, Salman

doi:10.1016/0009-2614(95)00213-n

Cited by 50 publications

(36 citation statements)

References 28 publications

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“…Recent experimental estimates of the OD/OH rate constant ratio place it in the range 1.3-1.5 for 300 K thermal rate measurements. 22,40,41 The comparison of the calculated results with experiment is clearly the closest for the K surface, and furthermore this represents a significant improvement over many other surfaces. 10 One further issue concerning the OD/OH ratio is the sensitivity of this ratio to trajectories which produce products with less than zero point energy in the vibration of the diatomic.…”

Section: Total Cross Sections Isotope Effects Rate Constantsmentioning

confidence: 61%

“…In particular, the SL surfaces favor a perpendicular insertion mechanism of O( 1 D) into H 2 while the MC surface favors a collinear abstraction one. Comparisons of quasi-classical trajectory ͑QCT͒ calculations 10 with new experimental data of the isotopic branching ratio and absolute rate coefficient, 22 as well as the data on the ͑inverted͒ OH vibrational distribution, 18,19 are in favor of the SL3 PES. The same conclusion was also reached by recent ab initio calculations of Walch and Harding.…”

Section: Introductionmentioning

confidence: 87%

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A global H2O potential energy surface for the reaction O(1D)+H2→OH+H

Hollebeek

Rabitz

et al. 1996

The Journal of Chemical Physics

182

172

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Articles you may be interested inAn ab initio analytical potential energy surface for the O(3 P)+CS(X 1Σ+)→CO(X 1Σ+)+S(3 P) reaction useful for kinetic and dynamical studies Thermal rate constants of the N2+O→NO+N reaction using ab initio 3 A″ and 3 A′ potential energy surfaces A global, single-valued ground-state H 2 O potential surface for the reaction O( 1 D)ϩH 2 →OHϩH has been constructed from a new set of accurate ab initio data using a general multidimensional interpolation method. The ab initio calculations are of the multireference, configuration interaction variety and were carried out using augmented polarized triple zeta basis sets. The multidimensional method is formulated within the framework of the reproducing kernel Hilbert space theory. The H 2 O potential is expressed as a many-body sum of a single one-body term, three two-body terms, and a single three-body term. The one-body term is the dissociation energy to the three-atom limit 2H( 2 S)ϩO( 3 P). The two-body terms are two O-H and one H-H adiabatic diatomic potentials of lowest energy. Each diatomic term is obtained by interpolating a discrete set of ab initio data using a one-dimensional, second-order, distancelike reproducing kernel. The three-body term is obtained by interpolating the difference of the H 2 O ab initio data and the one-and two-body sum by means of a direct product of three one-dimensional reproducing kernels on an optimized regular three-dimensional grid. The H 2 O potential energy surface is accurate, globally smooth, easy to evaluate, and asymptotically correct. Extensive quasiclassical trajectory calculations based on this new potential energy surface have been performed and compared with the results based on the potential energy surface of Murrell and Carter ͑MC͒ and that of Schinke and Lester ͑SL͒. Comparisons with recent experimental measurements on total cross sections, isotope effects, rate constants, vibrational, rotational, and angular distributions of the O( 1 D)ϩH 2 /HD reaction show that the new potential energy surface is a significant improvement over the MC and SL surfaces.

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Section: Total Cross Sections Isotope Effects Rate Constantsmentioning

confidence: 61%

Section: Introductionmentioning

confidence: 87%

A global H2O potential energy surface for the reaction O(1D)+H2→OH+H

Hollebeek

Rabitz

et al. 1996

The Journal of Chemical Physics

182

172

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“…In other studies 39 the integral cross section was found to decrease with increasing energy for energies below 2 kcal/mol ͑as expected for an insertion reaction with no barrier͒ and to increase at higher energies ͑as expected for an abstraction reaction͒. This influences the O͑ 1 D͒ϩH 2 rate coefficients, 29 and it is observed that the high temperature rate coefficient is substantially higher than at room temperature. This activated behavior is not expected for reaction on the ground state surface.…”

Section: Introductionmentioning

confidence: 87%

Quantum scattering study of electronic Coriolis and nonadiabatic coupling effects in O(1D)+H2→OH+H

Drukker

Schatz

1999

The Journal of Chemical Physics

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In this paper we develop an approximate quantum scattering method capable of determining cross sections for reactive A+BC collisions, with A being an open shell atom and BC being a closed shell diatomic molecule. This method is based on time-independent coupled channel calculations, and absorbing potentials are used to describe reaction. The coupled channel expansion includes all electronic states of the atom that correlate to a selected atomic term, and a converged set of rotational states of the diatomic. Diatomic vibration is approximated as an adiabatic degree of freedom. The method is used to study the title reaction, including all five of the electronic surfaces that correlate to O(1D)+H2 as well as terms in the Hamiltonian that couple these surfaces. These couplings include: electronic and rotational Coriolis coupling, and electrostatic nonadiabatic coupling. Coriolis coupling causes all five states to interact and is most important at long range, while electrostatic coupling produces strong interactions between the 11Σ and 11Π states at short range (where these states have a conical intersection) and weak but non-negligible interactions between these states at long range. The most important three of the five surfaces (11Σ and 11Π, or 11A′, 11A″ and 21A′) and the electrostatic nonadiabatic coupling between them are taken from the recent ab initio calculations of Dobbyn and Knowles [A. J. Dobbyn and P. J. Knowles, Mol. Phys. 91, 1107 (1997); Faraday Discuss. 110, 247 (1998)], while the other surfaces (11Δ or 21A″ and 31A′) are based on a diatomics-in-molecules potential. Our results for the fully coupled problem indicate that Coriolis coupling is significant between the electronic fine structure levels so that electronic alignment is not strongly preserved as the reactants approach. However, the fine structure averaged reaction probability is relatively insensitive to the electronic Coriolis mixing. Averaged reaction probabilities from a centrifugal decoupled calculation where both electronic and rotational Coriolis interactions are neglected are in good agreement (10% or better) with the results of the fully coupled calculations. We find that electrostatic nonadiabatic coupling between the lowest Σ and Π states is significant, even at energies below the Π barrier where only the long-range nonadiabatic coupling between these states is important. As a result, the low energy cross section summed over electronic states receives a ≈10% contribution from the Π state. We find that the total cross section decreases with energy for energies below ≈3.5 kcal/mol and increases slightly at higher energies, with the increase due to reaction over the Π barrier. We find that the Π barrier contribution to the cross section is about twice that obtained by treating the reaction adiabatically, with the difference due to nonadiabatic dynamics on the 21A′ state.

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“…Absolute rate constants and isotopic branching ratios have been reported (Laurent et al, 1995) for the reaction of O( 1 D) with HD. The k values were insigificantly different from the recommendation for H 2 , with a branching ratio OH/OD = 1.35 ± 0.20.…”

Section: Comments On Preferred Valuesmentioning

confidence: 99%

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of Ox, HOx, NOx and SOx species

et al. 2004

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Abstract. This article, the first in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of O x , HO x , NO x and SO x species, which were last published in 1997, and were updated on the IUPAC website in late 2001. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and five appendices containing the data sheets, which provide information upon which the recommendations are made.

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Absolute rate constants, reactive cross-sections and isotopic branching ratio for the reaction of O(1D) with HD

Cited by 50 publications

References 28 publications

A global H2O potential energy surface for the reaction O(1D)+H2→OH+H

A global H2O potential energy surface for the reaction O(1D)+H2→OH+H

Quantum scattering study of electronic Coriolis and nonadiabatic coupling effects in O(1D)+H2→OH+H

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of O<sub>x</sub>, HO<sub>x</sub>, NO<sub>x</sub> and SO<sub>x</sub> species

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Absolute rate constants, reactive cross-sections and isotopic branching ratio for the reaction of O(1D) with HD

Cited by 50 publications

References 28 publications

A global H2O potential energy surface for the reaction O(1D)+H2→OH+H

A global H2O potential energy surface for the reaction O(1D)+H2→OH+H

Quantum scattering study of electronic Coriolis and nonadiabatic coupling effects in O(1D)+H2→OH+H

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of O&lt;sub&gt;x&lt;/sub&gt;, HO&lt;sub&gt;x&lt;/sub&gt;, NO&lt;sub&gt;x&lt;/sub&gt; and SO&lt;sub&gt;x&lt;/sub&gt; species

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of O<sub>x</sub>, HO<sub>x</sub>, NO<sub>x</sub> and SO<sub>x</sub> species