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Spin‐forbidden reaction pathways in the interaction of singlet and triplet molecular oxygen with acetylene
Author(s) -
Trindle Carl,
Halevi E. A.
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560140727
Subject(s) - acetylene , chemistry , singlet state , spin (aerodynamics) , spin states , triplet state , dissociation (chemistry) , angular momentum , oxygen , symmetry (geometry) , singlet fission , molecular orbital , atomic physics , photochemistry , molecular physics , excited state , molecule , physics , quantum mechanics , inorganic chemistry , geometry , mathematics , organic chemistry , thermodynamics
The spin‐forbidden production of singlet molecular oxygen promoted by the complexation of triplet oxygen with acetylene is described with the aid of spin‐extended orbital correspondence analysis in maximum symmetry (OCAMS). It is shown that a strong collision complex is necessary to the change in spin state owing to angular momentum requirements. Two possible reaction pathways for the spin‐forbidden process are discerned; in both cases a rotation of O 2 relative to acetylene must accompany the approach to the O 2 ‐acetylene complex, and its subsequent dissociation. The sense of the rotation may in one case be parallel to the C 2 v (maximum) symmetry axis, and may in the other case be perpendicular to the plane of the complex four‐membered ring.