H+CO2→OH+CO: Yield versus HI photolysls wavelength and OH rotational distributions under single-collision conditions and with CO2HI complexes

Chen, Y.; Hoffmann, G. W.; Oh, Daniel S.; Wittig, C.

doi:10.1016/0009-2614(89)87511-6

Cited by 61 publications

(19 citation statements)

References 28 publications

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“…Using this information, we draw new conclusions about the PE surface which lead to a different picture· than the one derived by looking at the OH fragment alone. The internal energy of the OH fragment l l , 16,18,20,24,25 is in agreement with the predictions ofthe PE surface of Schatz et a/. 4 and also the statistical phase space calculations they quote.…”

Section: Introductionsupporting

confidence: 88%

“…Chen et al shortly thereafter reported reactive cross sections collected over a large range of H-atom energies, collected nascent OH distributions for five discrete H-atom energies and reported on OH rotational distribution generated from a vdW precursor for comparison to uncomplexed reactants. 25 Using H-atom energies of 2.6 eV, translational energies of nascent OH were reported for several J values in v" = O. These were found to be much higher (E T = 6380 cm -1) than expected based on statistical models.…”

Section: Introductionmentioning

confidence: 87%

“…These calculations assume that 19220 cm -1 is available in the H atom, which is based on the HS fragment being in v" = 0 following photodissociation at 193 nm. Actually, 68% of the hydrogen has this energy due to the vibrational distribution in HS, 32,33 however, based on the reactive cross sections obtained by Chen et al 25 the higher translational energies are more heavily favored.…”

Section: B Comparisons With Theoretically Determined Internal Energymentioning

confidence: 99%

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Nonstatistical CO product distributions from the hot H-atom reaction, H+CO2→OH+CO

Rice

Baronavski

1991

The Journal of Chemical Physics

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A quasiclassical trajectory study of the OH+CO reaction J. Chem. Phys. 95, 1635 (1991); 10.1063/1.461076 Investigation of OHH2 and OHCO reactions using argonsensitized pulse radiolysisThe hot H-atom reaction, H + e0 2 ..... OH + eo is investigated under several initial conditions designed to vary the angular momentum of the CO 2 reactant. The translationally hot H atoms are produced by photodissociating H 2 S at 193 nm, resulting in a reaction exoergicity of -120 kJ mol -1. The internal energy in the eo product is monitored by laser-induced fluorescence in the VUV spectral range. Under near-nascent conditions we report the rotational distributions of eo in v" = 0 under e0 2 reactant "temperatures" of 300, 70 and 40 K. Also reported are the rotational distributions of eo in V" = 1 at 300 K and 70 K and the population ratios of [v" = 1 ]I [v" = 0] at both initial CO 2 temperatures. Three distinctively "dynamical" aspects of the potential energy (PE) surface are exhibited in this set of experiments: (i) As the CO 2 reactant is cooled, a cooling of the eo distribution is seen which suggests the reaction intermediate does not live long enough to randomize its internal energy. (ii) We report a coupling of vibrational and rotational excitation in the CO product indicated by a "hotter" rotational energy in v" = 1 than v" = 0 at 300 K. (iiifln addition, we report different [v" = 1] / [v" = 0] ratios at the two CO 2 initial temperatures. eontrary to nearly all indications from measurements on the OH product, the CO product is rich in "nonstatistical" behavior.

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Section: Introductionsupporting

confidence: 88%

Section: Introductionmentioning

confidence: 87%

Section: B Comparisons With Theoretically Determined Internal Energymentioning

confidence: 99%

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Nonstatistical CO product distributions from the hot H-atom reaction, H+CO2→OH+CO

Rice

Baronavski

1991

The Journal of Chemical Physics

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“…To compare the experimental rotational state distributions of the product OH, [12][13][14] we have run more than 500 000 trajectories at the five experimental collision energies (1.35, 1.64, 1.86, 2.09, and 2.35 eV). At the lowest energy (1.35 eV), ∼1 260 000 trajectories were included in our calculations to reduce the statistical error.…”

Section: Final State Distributionsmentioning

confidence: 99%

“…The thermal rate constants for the title reaction indeed exhibit a clear Arrhenius behavior, 6,7 but are much smaller than its inelastic counterpart. 8 The subsequent research has focused on the cross sections and product distributions, [9][10][11][12][13][14][15][16][17] and multiple non-statistical features have been found for the reaction. More recently, attention has shifted to state-to-state reaction dynamics, [18][19][20][21] revealing surprisingly complex and rich dynamics.…”

Section: Introductionmentioning

confidence: 99%

Quasi-classical trajectory study of the H + CO2 → HO + CO reaction on a new ab initio based potential energy surface

Xie

Li²,

Xie

et al. 2012

The Journal of Chemical Physics

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A detailed quasi-classical trajectory study of the H + CO(2) → HO + CO reaction is reported on an accurate potential energy surface based on ab initio data. The influence of the vibrational and rotational excitations of CO(2) was investigated up to the collision energy of 2.35 eV. It was found that the total reaction integral cross section increases monotonically with the collision energy, consistent with experimental results. The excitation of the CO(2) bending vibration enhances the reaction, while the excitation in its asymmetric stretching vibration inhibits the reaction. The calculated thermal rate constants are in excellent agreement with experiment. At the state-to-state level, the rotational state distributions of the HO product are in good agreement with experimental results, while those for the CO product are much hotter than measurements. The calculated differential cross sections are dominated by forward scattering, suggesting that the lifetime of the HOCO intermediate may not be sufficiently long to render the reaction completely statistical.

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Photoinitiated Reactions in Weakly Bonded Complexes

Wittig

1991

Advances in Photochemistry

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H+CO2→OH+CO: Yield versus HI photolysls wavelength and OH rotational distributions under single-collision conditions and with CO2HI complexes

Cited by 61 publications

References 28 publications

Nonstatistical CO product distributions from the hot H-atom reaction, H+CO2→OH+CO

Nonstatistical CO product distributions from the hot H-atom reaction, H+CO2→OH+CO

Quasi-classical trajectory study of the H + CO2 → HO + CO reaction on a new ab initio based potential energy surface

Photoinitiated Reactions in Weakly Bonded Complexes

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