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Peroxone chemistry: Formation of H_2O_3 and ring-(HO_2)(HO_3) from O_3/H_2O_2

Xu, Xin and Goddard, William A., III (2002) Peroxone chemistry: Formation of H_2O_3 and ring-(HO_2)(HO_3) from O_3/H_2O_2. Proceedings of the National Academy of Sciences of the United States of America, 99 (24). pp. 15308-15312. ISSN 0027-8424. PMCID PMC137712. doi:10.1073/pnas.202596799.

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The recent observation [Wentworth, P., Jones, L. H., Wentworth, A. D., Zhu, X. Y., Larsen, N. A., Wilson, I. A., Xu, X., Goddard, W. A., Janda, K. D., Eschenmoser, A. & Lerner, R. A. (2001) Science 293, 1806–1811] that antibodies form H_2O_2 from ^1O_2 plus H_2O was explained in terms of the formation of the H_2O_3 species that in the antibody reacts with a second H_2O_3 to form H_2O_2. There have been few reports of the chemistry for forming H_2O_3, but recently Engdahl and Nelander [Engdahl, A. & Nelander, B. (2002) Science 295, 482–483] reported that photolysis of the ozone–hydrogen peroxide complex in argon matrices leads to significant concentrations of H_2O_3. We report here the chemical mechanism for this process, determined by using first-principles quantum mechanics. We show that in an argon matrix it is favorable (3.5 kcal/mol barrier) for H_2O_2 and O_3 to form a [(HO_2)(HO_3)] hydrogen-bonded complex [head-to-tail seven-membered ring (7r)]. In this complex, the barrier for forming H_2O_3 plus ^3O_2 is only 4.8 kcal/mol, which should be observable by means of thermal processes (not yet reported). Irradiation of the [(HO_2)(HO_3)-7r] complex should break the HO–OO bond of the HO_3 moiety, eliminating ^3O_2 and leading to [(HO_2)(HO)]. This [(HO_2)(HO)] confined in the matrix cage is expected to rearrange to also form H_2O_3 (observed experimentally). We show that these two processes can be distinguished isotopically. These results (including the predicted vibrational frequencies) suggest strategies for synthesizing H_2O_3 and characterizing its chemistry. We suggest that the [(HO_2)(HO_3)-7r] complex and H_2O_3 are involved in biological, atmospheric, and environmental oxidative processes.

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Goddard, William A., III0000-0003-0097-5716
Alternate Title:Peroxone chemistry: Formation of H2O3 and ring-(HO2)(HO3) from O3/H2O2
Additional Information:© 2002 National Academy of Sciences. Contributed by William A. Goddard III, October 2, 2002. Published ahead of print November 18, 2002. We thank Prof. Richard Lerner for pointing out the peroxone process and some references to us. This research was funded by National Institutes of Health Grant HD 36385-02 and the National Science Foundation. The facilities of the Materials and Process Simulation Center used in these studies were funded by a Shared University Research Grant from IBM and grants from the Defense University Research Instrumentation Program (Army Research Office and Office of Naval Research) and the National Science Foundation Major Research Instrumentation. In addition, the Materials and Process Simulation Center is funded by grants from the Department of Energy–Accelerated Strategic Computing Initiative–Academic Strategic Alliances Program, Army Research Office Multidisciplinary University Research Initiative, National Institutes of Health, National Science Foundation, ChevronTexaco, Seiko-Epson, Kellogg’s, 3M, Asahi Kasei, Nippon Steel, and Toray.
Funding AgencyGrant Number
NIHHD 36385-02
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
Issue or Number:24
PubMed Central ID:PMC137712
Record Number:CaltechAUTHORS:20141121-133241067
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Official Citation:Xin Xu and William A. Goddard III Peroxone chemistry: Formation of H2O3 and ring-(HO2)(HO3) from O3/H2O2 PNAS 2002 99 (24) 15308-15312; published ahead of print November 18, 2002, doi:10.1073/pnas.202596799
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:52051
Deposited By: Tony Diaz
Deposited On:21 Nov 2014 21:48
Last Modified:10 Nov 2021 19:20

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