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>Theoretical studies of the ozone molecule. I.AbinitioMCSCF/CI potential energy surfaces for theXthinsp;1A1andathinsp;2B2states
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Theoretical studies of the ozone molecule. I.AbinitioMCSCF/CI potential energy surfaces for theXthinsp;1A1andathinsp;2B2states
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机译：Theoretical studies of the ozone molecule. I.AbinitioMCSCF/CI potential energy surfaces for theXthinsp;1A1andathinsp;2B2states
The potential energy surfaces for theXthinsp;1A1and firsthyphen;excitedathinsp;3B2states of ozone are surveyed with accurateabinitioelectronic structure calculations. An efficient technique for using the multiconfiguration selfhyphen;consistent field (MCSCF) method for polyatomics has been established for these computations, and is described in some detail. The method involves a geometryhyphen;dependent flow of configurations between the MCSCF wave function and a small configuration interaction (CI) wave function. The configurations are constructed in a set of 8 core, 7 valence, and 4 rsquo;rsquo;virtualrsquo;rsquo; MCSCF orbitals, which are expanded in a doublehyphen;zeta plus polarization onehyphen;electron basis. The vertical and adiabatic excitation energies, uncorrected for zerohyphen;point energies, are presently obtained as 1.21 and 0.74 eV, respectively. These results are in agreement with other quantitative theoretical studies which are now available for comparison. Furthermore, the present results indicate that O3(athinsp;3B2) has an O2ndash;O binding energyEb=0.4 eV and that there is no barrier relative to its adiabatic asymptote, O(3P)+O2(Xthinsp;3Sgr;minus;g). These energies are estimated to be accurate to within 0.2 eV. Thus, we conclude that O3(athinsp;3B2) is a bound state of ozone. Similar MCSCF/CI calculations are reported for the ring state. The implications of this work for ozone chemistry are discussed. The existence of a second bound state, relative to the ground state atomndash;diatomic asymptote, may have important consequences with regard to the interpretation and modeling of ozone formation from O(3P) and O2(Xthinsp;3Sgr;minus;g): theathinsp;3B2state, as well as theXthinsp;1A1state, may be involved.
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