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Quasi-classical trajectory study of the H + CO2 → HO + CO reaction on a new ab initio based potential energy surface
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10.1063/1.4733334
/content/aip/journal/jcp/137/2/10.1063/1.4733334
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/2/10.1063/1.4733334

Figures

Image of FIG. 1.
FIG. 1.

Energetic of reaction pathways for the H + CO2 ↔ HO + CO reaction. The ab initio energies of the stationary points are given in eV. The zero of the energy is corresponding to the trans-HOCO potential minimum.

Image of FIG. 2.
FIG. 2.

Contour plot of the PES for H approaching CO2, which is placed on the x axis, with all other degrees of freedom optimized. The two transition states (TS2 and TS3) are shown by red dots. The energy scale is given in kcal/mol.

Image of FIG. 3.
FIG. 3.

Total ICSs for the H + CO2 → HO + CO reaction. (a) Total ICSs of the ground rovibrational CO2 as a function of the collision energy. The experimental curve of Hoffmann et al. 14 is taken from Ref. 28, and the one of Jacobs et al. is from Ref. 12. The theoretical results of Troya et al. are from Ref. 34. (b) Total ICSs as a function of the total energy for the ground rovibrational state, the ground vibrational state with a 300 K rotational temperature, and of several low-lying vibrational excited states of CO2.

Image of FIG. 4.
FIG. 4.

Comparison of calculated rate constants for several lowest-lying vibrational states of CO2 and the Boltzmann averaged values between 1000 and 3000 K. The experimental values from Refs. 6 and 7 are also included for comparison.

Image of FIG. 5.
FIG. 5.

The rotational state distributions of the HO product at five collision energies (1.35, 1.64, 1.86, 2.09, and 2.35 eV). The experimental results from Refs. 14 and 12 and the theoretical results on the LTSH PES at 1.86 and 2.35 eV are also included for comparison and they are normalized to the maxima of our results.

Image of FIG. 6.
FIG. 6.

The rotational distributions of the CO (v = 0 and 1) product at three collision energies (1.86, 2.09, and 2.35 eV). The experimental results from Ref. 15 and 16 and the theoretical results on the LTSH PES at 2.35 eV are also included for comparison and they are normalized to the maxima of our results.

Image of FIG. 7.
FIG. 7.

Translational energy distributions of the H + CO2 → HO + CO reaction at five collision energies (1.35, 1.64, 1.86, 2.09, and 2.35 eV).

Image of FIG. 8.
FIG. 8.

Total DCSs of the H + CO2 → HO + CO reaction at five collision energies (1.35, 1.64, 1.86, 2.09, and 2.35 eV).

Tables

Generic image for table
Table I.

Geometry parameters (in Å and deg) of the stationary points along the HO + CO ↔ H + CO2 reaction paths. The six geometry parameters are the internal coordinates with O initially bonded to C of CO.

Generic image for table
Table II.

Electronic energies (kcal/mol) and harmonic frequencies (cm−1) of the pertinent stationary points along the HO + CO ↔ H + CO2 reaction paths.

Generic image for table
Table III.

Lifetimes of the HOCO intermediate for the reactive trajectories and comparison with RRKM results.14

Generic image for table
Table IV.

Comparison of energy partitioning for the HO + CO → H + CO2 reaction using different theories.

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/content/aip/journal/jcp/137/2/10.1063/1.4733334
2012-07-11
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Quasi-classical trajectory study of the H + CO2 → HO + CO reaction on a new ab initio based potential energy surface
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/2/10.1063/1.4733334
10.1063/1.4733334
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