Water-catalyzed gas-phase hydrogen abstraction reactions of CH3O2 and HO2 with HO2: a computational investigationElectronic supplementary information (ESI) available: The scheme of possible reaction pathways, T1 diagnostic values, energetic information and vibrational frequencies for water-catalyzed gas-phase reactions of CH3O2 and HO2 with HO2 are listed in Fig. S1, Table S1, Tables S2 and S3 and Tables S4 and S5, respectively. Fig. S3 shows the optimized geometrical structures for the species
The gas-phase hydrogen abstraction reactions of CH 3 O 2 and HO 2 with HO 2 in the presence and absence of a single water molecule have been studied at the CCSD(T)/6-311++G(3d,2p)//B3LYP/6-311G(2d,2p) level of theory. The calculated results show that the process for O 3 formation is much faster than...
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| Main Authors | , , , , |
|---|---|
| Format | Journal Article |
| Language | English |
| Published |
15.11.2011
|
| Online Access | Get full text |
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| Summary: | The gas-phase hydrogen abstraction reactions of CH
3
O
2
and HO
2
with HO
2
in the presence and absence of a single water molecule have been studied at the CCSD(T)/6-311++G(3d,2p)//B3LYP/6-311G(2d,2p) level of theory. The calculated results show that the process for O
3
formation is much faster than that for
1
O
2
and
3
O
2
formation in the water-catalyzed CH
3
O
2
+ HO
2
reaction. This is different from the results for the non-catalytic reaction of CH
3
O
2
+ HO
2
, in which almost only the process for
3
O
2
formation takes place. Unlike CH
3
O
2
+ HO
2
reaction in which the preferred process is different in the catalytic and non-catalytic conditions, the channel for
3
O
2
formation is the dominant in both catalytic and non-catalytic HO
2
+ HO
2
reactions. Furthermore, the calculated total CVT/SCT rate constants for water-catalyzed and non-catalytic title reactions show that the water molecule doesn't contribute to the rate of CH
3
O
2
+ HO
2
reaction though the channel for O
3
formation in this water-catalyzed reaction is more kinetically favorable than its non-catalytic process. Meanwhile, the water molecule plays an important positive role in increasing the rate of HO
2
+ HO
2
reaction. These results are in good agreement with available experiments.
The singlet water molecule doesn't contribute to the rate of CH
3
O
2
+ HO
2
reaction whereas it increases the rate of HO
2
+ HO
2
reaction drastically. |
|---|---|
| Bibliography: | with and without a water molecule are described in Fig. S2 and Fig. S4, respectively. Besides, Table S6 displays the calculated CVT/SCT rate constants of Path a and Path c′ along with the available experimental and theoretical values; Fig. S5 shows a schematic energy diagram for Path aw3 and aw4 that are involved in Channel aw. See DOI 10.1039/c1cp21563a with HO HO H O) and products (CH at several different levels of theory, whereas optimized geometries of all the species in the reaction of CH Electronic supplementary information (ESI) available: The scheme of possible reaction pathways, T1 diagnostic values, energetic information and vibrational frequencies for water-catalyzed gas-phase reactions of CH O 2 and HO 3 are listed in Fig. S1, Table S1, Tables S2 and S3 and Tables S4 and S5, respectively. Fig. S3 shows the optimized geometrical structures for the species of the reactants (HO OH |
| ISSN: | 1463-9076 1463-9084 |
| DOI: | 10.1039/c1cp21563a |