ESR and IR Study of ClOO Exchange-Coupled to O2

Photolysis below 100 K of the exchange-coupled complex [OClO,O2] in KClO4 at λ ≈ 365 nm yields a metastable product, already identified earlier as the complex [ClO,O3] and also a stable product that we identify as an exchange-coupled complex of ClOO and O2. The 17O hyperfine splitting of the ESR spe...

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Bibliographic Details
Published in:Journal of physical chemistry (1952) 1996-05, Vol.100 (22), p.9247-9249
Main Author: Byberg, J. R
Format: Article
Language:English
Online Access:Get full text
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Summary:Photolysis below 100 K of the exchange-coupled complex [OClO,O2] in KClO4 at λ ≈ 365 nm yields a metastable product, already identified earlier as the complex [ClO,O3] and also a stable product that we identify as an exchange-coupled complex of ClOO and O2. The 17O hyperfine splitting of the ESR spectrum serves to verify the presence of O2 and the overall spin-doublet ground state of the complex, while the O−O stretching frequency ν1 is used as a fingerprint of ClOO. The observed value of ν1, the principal values of the spin Hamiltonian parameter matrices, and the structural clues conveyed by the direction of the principal axes with respect to the lattice all indicate that ClOO retains its integrity in the complex [ClOO,O2] despite the extreme weakness of the Cl−O bond.
ISSN:0022-3654
1541-5740
DOI:10.1021/jp9527012