ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Ab initio molecular orbital calculations have been used to study the most important features of the potential energy surfaces corresponding to Li+ association to C2v and D3h ozone. For this purpose highly correlated techniques [CASSCF, QCISD, and QCISD(T)] have been used. Our results confirm that these highly correlated techniques are unavoidable in so far as a correct description of ozone–Li+ complexes is needed. Good agreement between CASSCF and QCI results is attained for C2v ozone when the UHF function is taken as the reference function and triple excitations are considered in the QCI treatment. Results for D3h ozone are in agreement only when a proper description of the π correlation is included in the CASSCF treatment. Interactions with Li+ are stronger for open chain ozone than for the cyclic isomer. Thus on complex formation the energy gap between C2v and D3h ozone increases. There exist three structures which are predicted to lie very close in energy. The global energy minimum corresponds to an isomer in which the Li+ bridges both terminal oxygens, but other structures corresponding to the attachment of Li+ to one of the terminal oxygens and to an insertion of the Li+ in one of the O–O bonds, respectively, are about 1 kcal/mol less stable. © 1995 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.469638
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