Ab initio calculations of the potential energy surface (PES) for the BrϩO 3 reaction have been performed using the MP2, CCSD(T), and QCISD(T) methods with 6-31G(d), 6-311G(d), and 6-311ϩG(3df). The reaction begins with a transition state (TS) when the Br atom attacks a terminal oxygen of ozone, producing an intermediate, the bromine trioxide (M), which immediately dissociates to BrOϩO 2 . The geometry optimizations of the reactants, products, and intermediate and transition states are carried out at the MP2/6-31G(d) level. The reaction potential barrier is 3.09 kcal/mol at the CCSD(T)/6-311ϩG(3df)//MP2 level, which shows that the bromine atom trends intensively to react with the ozone. The comparison of the BrϩO 3 reaction with the FϩO 3 and ClϩO 3 reactions indicates that the reactions of ozone with the halogen atoms have the similar reaction mechanism.
The structures and stabilities of a new class of species, noble-gas-coinage-metal hydroxides NgMOH (Ng ¼ Ar, Kr and Xe; M ¼ Cu and Ag), are investigated at the MP2 theoretical level. All species are found to be in Cs symmetry with an approximate linear Ng-M-O moiety. The noble-gas-coinage-metal bond lengths are in the range of the respective covalent and van der Waals limits, showing a different degree of approach to the former along the series Ar-Kr-Xe for Ng-Cu and Ng-Ag bonds, respectively. The dissociation energies of noble-gas-coinage-metal bonds are relatively large as compared to the van der Waals complexes. Besides the charge-induced dipole contribution, other effects -higher-order charge-induction energies, dispersion interaction, etc., should be considered to explain the noble-gas-coinage-metal bonding mechanism. The present results suggest that the title species are stable enough to be prepared experimentally.
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