Experimental and theoretical study of the recombination reaction FSO 2 + O 2 → FS(O 2)OO
FSO 3 absorbance recorded at 450 nm following the 193 nm photolysis of FS(O 2)O(O 2)SF. The addition of O 2 modifies the decay due to the reaction FSO 2 + O 2 → FS(O 2)OO. The kinetics of the recombination reaction FSO 2 + O 2 → FS(O 2)OO (1) has been studied at 298 K. FSO 2 together with FSO 3 radi...
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Published in | Chemical physics letters Vol. 465; no. 1; pp. 15 - 19 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
Elsevier B.V
2008
|
Online Access | Get full text |
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Summary: | FSO
3 absorbance recorded at 450
nm following the 193
nm photolysis of FS(O
2)O(O
2)SF. The addition of O
2 modifies the decay due to the reaction FSO
2
+
O
2
→
FS(O
2)OO.
The kinetics of the recombination reaction FSO
2
+
O
2
→
FS(O
2)OO
(1) has been studied at 298
K. FSO
2 together with FSO
3 radicals were generated by 193
nm laser flash photolysis of FS(O
2)O(O
2)SF. The measured rate coefficient at one atmosphere total pressure is
k
1
=
(4.6
±
0.6)
×
10
−15
cm
3
molecule
−1
s
−1. Molecular properties for the FS(O
2)OO radical were calculated at the B3LYP/6-311+G(3df) and CCSD/6-311G(d) levels of theory. Consistent with the measured
k
1 value, different density functional theory and G
aussian-3 calculations predict an electronic energy barrier for reaction
(1) close to 3
kcal
mol
−1. |
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ISSN: | 0009-2614 1873-4448 |
DOI: | 10.1016/j.cplett.2008.09.033 |