Singlet oxygen photogeneration from X-O2 van der Waals complexes: double spin-flip vs. charge-transfer mechanism
The channel of singlet oxygen O 2 ( 1 Δ g ) photogeneration from van der Waals complexes of oxygen X-O 2 has been investigated to discriminate between two possible mechanisms based on charge-transfer (CT) or double spin-flip (DSF) transitions. The results obtained in this work for complexes with X =...
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Published in | Physical chemistry chemical physics : PCCP Vol. 17; no. 43; pp. 28565 - 28573 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
Published |
England
21.11.2015
|
Online Access | Get full text |
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Summary: | The channel of singlet oxygen O
2
(
1
Δ
g
) photogeneration from van der Waals complexes of oxygen X-O
2
has been investigated to discriminate between two possible mechanisms based on charge-transfer (CT) or double spin-flip (DSF) transitions. The results obtained in this work for complexes with X = ethylene C
2
H
4
, 1,3-butadiene C
4
H
6
, deuterated methyl iodide CD
3
I, benzene C
6
H
6
and water H
2
O and for those investigated previously indicate the DSF mechanism as a source of singlet oxygen. The formation of O
2
(
1
Δ
g
) is observed only when the energy of exciting quantum is sufficient for DSF transition. Universally detected low vibrational excitation of O
2
(
1
Δ
g
) arising in the photodissociation of van der Waals complexes X-O
2
indicates the DSF mechanism as its source. For complex of ethylene C
2
H
4
-O
2
ab initio
calculations of vertical energy Δ
E
vert
for DSF and CT transitions have been carried out. The positive results of singlet oxygen formation from C
2
H
4
-O
2
can be explained by the DSF but not by the CT mechanism.
The channel of singlet oxygen O
2
(
1
Δ
g
) photogeneration from van der Waals complexes of oxygen X-O
2
has been investigated to discriminate between two mechanisms based on charge-transfer or double spin-flip transitions. |
---|---|
Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1463-9076 1463-9084 |
DOI: | 10.1039/c5cp03129j |