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Geometry and electronic structure of the hydroperoxyl radical.

by Dean H Liskow, Henry F I I I Schaefer, Charles F Bender
J. Amer. Chem. Soc. ()
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Ab initio SCF and configuration-interaction (CI) calcns. were crried out to investigate the geometry and electronic structure of the 2A'' ground state of the HO2 radical. A slightly better than double-{Î}\textparagraph basis set of contracted Gaussian functions was used. First-order wave functions including 500 configurations were used to describe electron correlation in HO2. The iterative natural orbital procedure was used to generate an optimum set of MO. The SCF predicted geometry is r(H-O)=0.968 {Ã}…, r(O-O)=1.384 {Ã}…, and bond angle 106.8{Â}\textdegree. The 1st-order geometry is r(O-H)=0.973 {Ã}…, r(O-O)=1.458 {Ã}…, and bond angle 104.6{Â}\textdegree. Our bond angle is consistent with Walsh's prediction, and the overall geometry is in essential accord with that suggested by Paukert and Johnston. However, several earlier theoretical predictions are not consistent with our results. Force consts. are predicted which suggest that the O-H bond is similar to that in water, but the O-O bond is much weaker than that in the O2 mol. The H-O2 dissocn. energy is predicted to 2.36 eV in the SCF approxn. and 2.82 eV from CI, compared to an exptl. value of 2 eV. The electronic structure of HO2 is discussed in terms of the natural orbital occupation nos. and the most important configurations. [on SciFinder(R)]

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