Protonated Ozone: Experimental Detection of O ₃ H ⁺ and Evaluation of the Proton Affinity of Ozone

Abstract

The elusive protonated ozone ion (O(3)H(+)) has been long postulated as a reactive intermediate but never experimentally observed. This ion has been detected here in mass spectrometric experiments with the use of Fourier transform ion cyclotron resonance. In these experiments, ozone (O(3)) was protonated by strong acids-for example, H(3)(+), KrH(+), XeH(+), and CH(5)(+). The hitherto experimentally unknown proton affinity of O(3) was evaluated by a "bracketing" technique and determined to be 148 -/+ 3 kilocalories mole(-1) at 298 kelvin, in excellent agreement with a value determined in a recent theoretical study of the O(3)/O(3)H(+) system, which was 148 kilocalories mole(-1) at zero temperature ( approximately 149.5 kilocalories mole(-1) at 298 kelvin).

Evidence for the production of trioxygen species during antibody-catalyzed chemical modification of antigens

“…The hydrotrioxide radical has been postulated to be an important intermediate in atmospheric processes (16), but it was not clear whether after formation it would dissociate immediately into 3 O 2 and HO • (17,18). However, HO 3 • has recently been detected experimentally by both Speranza (19) and Cacace and coworkers (20,21) using Fourier-transform ion cyclotron resonance mass spectrometry and neutralizationreionization mass spectrometry, respectively, and its lifetime has been calculated to be of the order of microseconds. Our own qualitative chemical reasoning as well as quantum chemical calculations point to the potential of the HO 3 • or the [HO 2…”

Protonation of the ozone analogue S2O: structures, energies and vibrational spectra of HS2O+isomers

“…For SSO the protonation energies for attachment at the two ends di er by only 12.6 kcal mol -1 at the TZ2P/CISD level (173.0 at sulphur, 186.2 at oxygen, cis), despite the di erence in electronegativity between oxygen and sulphur. The protonation energy of the central sulphur (141.0 kcal mol -1 at TZ2P/CISD) is similar to the proton a nities of ozone, i.e., 148 kcal mol -1 (theory) [8] and 149.5 kcal mol -1 (experiment) [9]. The proton a nity of S 3 is found theoretically by Toscano, Russo and Rubio [32] to be 178.2 kcal mol -1 .…”

“…For ozone, accurate theoretical determination of even ground state properties has proved di cult [ 1± 7]. Recent studies of these molecules have focused on protonation reactions, the relative energies of various excited states, and the relative energies of geometric isomers, including an impressive success for theory in the prediction of a protonation energy of 148 kcal mol -1 for ozone obtained by Meridith, Quelch, and Schaefer [8] which subsequently was found experimentally to be 148 6 3 kcal mol -1 by Cacace and Speranza [9]. Lee obtained the ring-open chain energy di erence for O 3 at high levels of theory [10].…”

Potential energy surfaces of C2v and D3h ozone complexes with Li+

“…5 Its Brønsted-base character has been recently proven by the detection of the corresponding Brønsted acid ͑O 3 H ϩ ͒ and the determination of its proton affinity. 6 Li ϩ represents one of the simplest Lewis acids, and the study of its reactivity with ozone can give some new insights to the behavior of the ozone as a Lewis base and the differences with respect its Brønsted base character.…”