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Dynamics of the reactions of O(1D) with CD3OH and CH3OD studied with time-resolved Fourier-transform IR spectroscopy
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10.1063/1.4759619
/content/aip/journal/jcp/137/16/10.1063/1.4759619
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/16/10.1063/1.4759619

Figures

Image of FIG. 1.
FIG. 1.

Observed IR emission spectra of the reaction system O(1D)+ CD3OH recorded at 1-μs intervals. The spectral resolution is 0.8 cm−1. Partial pressures of O3 and CD3OH are 0.018−0.022 and 0.104−0.106 Torr, respectively. The assignments of vibration-rotational transitions are shown as stick diagrams for OH and OD, respectively; the numbers correspond to J .

Image of FIG. 2.
FIG. 2.

Semilogarithmic plots of the rotational populations of OH and OD as a function of the rotational energy in respective vibrational levels formed from the O(1D)+CD3OH reaction. Average period is 0−5 μs.

Image of FIG. 3.
FIG. 3.

Plot of rotational temperature of OD (v = 1−3) as a function of time. The data extrapolated to t = 0 are indicated with o.

Image of FIG. 4.
FIG. 4.

Relative vibrational populations of OH and OD produced from the O(1D) + CD3OH reaction (a) and O(1D) + CH3OD reaction (b) as a function of vibrational quantum number v. Populations in v = 0 are derived by extrapolation.

Image of FIG. 5.
FIG. 5.

Observed IR emission spectra of the reaction system O(1D)+CH3OD recorded at 1-μs intervals. The spectral resolution is 0.8 cm−1. Partial pressures of O3 and CH3OD are 0.018−0.022 and 0.104−0.106 Torr, respectively. The assignments of vibration-rotational transitions in P branches are given as stick diagrams for OH and OD, respectively; the numbers correspond to J .

Image of FIG. 6.
FIG. 6.

Semilogarithmic plots of the rotational populations of OH and OD as a function of the rotational energy in respective vibrational levels formed from the O(1D) + CH3OD reaction. Average period is 0−5 μs.

Image of FIG. 7.
FIG. 7.

Simplified potential-energy scheme for production of OH and H in the reaction O(1D) + CH3OH computed with the CCSD(T)//B3LYP/aug-cc-pVTZ method. TS indicate transition states. Energy is in kJ mol−1.

Image of FIG. 8.
FIG. 8.

Geometry of CH3O(O)H, trans-HOCH2OH, cis-HOCH2OH, CH3OOH and transition states TS1/2S, TS3/4S, TSa and TSb predicted with the B3LYP/aug-cc-pVTZ method. Bond lengths are in Å and bond angles are in deg.

Image of FIG. 9.
FIG. 9.

Predicted microcanonical rate coefficients for reactions O(1D) + CH3OD (a) and O(1D) + CD3OH (b) as a function of excess energy relative to reactants.

Image of FIG. 10.
FIG. 10.

Predicted k OH/k OD for reactions O(1D) + CH3OD and O(1D) + CD3OH as a function of excess energy relative to reactants.

Image of FIG. 11.
FIG. 11.

Predicted ratios k H/k D for reactions O(1D) + CH3OD and O(1D) + CD3OH as a function of excess energy relative to reactants.

Tables

Generic image for table
Table I.

Summary of experimental results for reactions O(1D) + CH3OD/CD3OH.

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/content/aip/journal/jcp/137/16/10.1063/1.4759619
2012-10-24
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Dynamics of the reactions of O(1D) with CD3OH and CH3OD studied with time-resolved Fourier-transform IR spectroscopy
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/16/10.1063/1.4759619
10.1063/1.4759619
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