The vibrational spectrum of H2O3: An ab initio investigation

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Abstract
Theoretically determined frequencies and absorption intensities are reported for the vibrational spectra of the covalent HOOOH and hydrogen bonded HO...HOO intermediates that may form in the reaction of the hydroxyl and hydroperoxyl radicals. Basis sets of double-zeta-polarized quality, augmented by diffuse and second sets of polarization functions have been used with complete-active-space, self-consistent-field wave functions. The calculated harmonic vibrational frequencies of HOOOH have been corrected with empirical factors and presented in the form of a ‘‘stick’’ spectrum. The oxygen backbone vibrations, predicted to occur at 519, 760, and 870 cm−1, are well separated from most interferences, and may be the most useful for the species’ identification. In the case of the hydrogen bonded isomer, emphasis has been placed upon prediction of shifts in the intramolecular vibrational frequencies that take place upon formation of the complex. In particular, the HO stretch and HOO bend of HO2 are predicted to have shifts of −59 and 53 cm−1, respectively, which should facilitate their identification. It is also noted that the antisymmetric stretching frequency of the oxygen backbone in HOOOH exhibits a strong sensitivity to the degree of electron correlation, similar to that which has been previously observed for ozone.

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