Kinetics of the reaction between hydroxyl and hydroperoxyl on the singlet potential energy surface

Gonzalez, C.; Theisen, John; Zhu, Liping; Schlegel, H. Bernhard; Hase, William L.; Kaiser, E. W.

doi:10.1021/j100171a010

Cited by 54 publications

(82 citation statements)

References 3 publications

(5 reference statements)

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“…This then proceeds to similar products. For a system with 18 The results lead to plausible mechanisms in good agreement with the Scripps isotope experiments. The Discussion talks about these results, suggesting that these mechanisms account for the Scripps Ab results and they may also be significant for understanding related processes in biochemistry, combustion, explosions, atmospheric chemistry, and radiation chemistry of aqueous systems.…”

supporting

confidence: 71%

“…The net result is 3.5 HOOH ϩ 4.0 HOO*H ϩ 0.5 (HO*O*H), leading to an overall 16 O: 18 O ratio of 11:5 ϭ 2.2:1 in the two HOOH products. This is in excellent agreement with the experimental value of 2.2:1, giving strong support to this mechanism.…”

Section: Reaction Of Hoooh With Hoooh (Pathway I) Direct Conversion Tomentioning

confidence: 99%

“…5 is lost and replaced with 18 The net result is 3.5 HOOH ϩ 3.0 HOO*H ϩ 1. Adding H 2 O to the HOOH-OOO in Eq.…”

Section: Reaction Of Hoooh With Hoooh (Pathway I) Direct Conversion Tomentioning

confidence: 99%

“…1 leads to one 18 18 O next to an H and one away from it so that the product HOOH has one 18 O. Thus, the net result is that the two HOOH products have a total of three 16 O and one 18 O, leading to a 3:1 ratio. This is in the range of the experiments, but probably on the high side.…”

Section: Summary Of the H2o3 Plus 1 O2 Mechanism (Pathway Ii)mentioning

confidence: 99%

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The gas phase reaction of singlet dioxygen with water: A water-catalyzed mechanism

Muller

Goddard

2002

Proc. Natl. Acad. Sci. U.S.A.

105

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Abs efficiently catalyze the conversion of molecular singlet oxygen ( 1 O2) plus water to hydrogen peroxide (HOOH), we used quantum chemical methods (B3LYP density functional theory) to delineate the most plausible mechanisms for the observed efficient conversion of water to HOOH. We find two reasonable pathways. In Pathway I, (i) H2O catalyzes the reaction of 1 O2 with a second water to form HOOOH; (ii) two HOOOH form a dimer, which rearranges to form the HOO-HOOO ؉ H2O complex; (iii) HOO-HOOO rearranges to HOOH-OOO, which subsequently reacts with H2O to form H2O4 ؉ HOOH; and (iv) H2O4 rearranges to the cyclic dimer (HO2)2, which in turn forms HOOH plus 1 O2 or 3 O2. Pathway II differs in that step ii is replaced with the reaction between HOOOH and 1 O2, leading to the formation of HOO-HOOO. This then proceeds to similar products. For a system with 18 The results lead to plausible mechanisms in good agreement with the Scripps isotope experiments. The Discussion talks about these results, suggesting that these mechanisms account for the Scripps Ab results and they may also be significant for understanding related processes in biochemistry, combustion, explosions, atmospheric chemistry, and radiation chemistry of aqueous systems. Computational DetailsAll QM calculations use the Becke three-parameter hybrid functional with Lee-Yang-Parr correlation functional (B3LYP) flavor of density functional theory (3-7), which includes a generalized gradient approximation and some exact exchange. The 6-31G** basis set (8, 9) was used on all atoms for a full geometry optimization. Vibrational frequencies (from the analytic Hessian) were calculated to ensure that each minimum is a true local minimum (containing only positive frequencies) and that each transition state has only a single imaginary frequency (negative eigenvalue of the Hessian). All QM calculations were carried out with JAGUAR (10-12). Some of these energetics were included in ref. 2.To obtain more accurate energetics, we carried out calculations with the cc-pVTZ basis set (13) by using the optimized geometries from the 6-31G** basis. Such QM calculations lead to an accuracy of around 3 kcal͞mol for simple organic molecules (14).For molecules such as 1 O 2 and O 3 , which have significant open shell character, standard density functional theory methods often lead to much larger errors. Thus, with B3LYP, the singlet and triplet gap for O 2 is ⌬E ( 1 ⌬ g Ϫ 3 ⌺ g Ϫ ) ϭ 10.4 kcal͞mol, in poor agreement with the experimental value of 22.5 kcal͞mol (15). Consequently, we used spin projection techniques (16) to ensure a proper description of the complexes involving 1 O 2 . This leads to ⌬E ( 1 ⌬ g Ϫ 3 ⌺ g Ϫ ) ϭ 20.5 kcal͞mol, in good agreement with experiment.The calculated vibrational frequencies (with no empirical scaling) were used to calculate the zero point energy and temperature corrections so that all energetics are reported for ⌬H (298K), in kcal͞mol. QM Calculations and Plausible MechanismsFormation of H2O2 from the Reaction Between Two H2O3. First, we examined...

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supporting

confidence: 71%

Section: Reaction Of Hoooh With Hoooh (Pathway I) Direct Conversion Tomentioning

confidence: 99%

“…5 is lost and replaced with 18 The net result is 3.5 HOOH ϩ 3.0 HOO*H ϩ 1. Adding H 2 O to the HOOH-OOO in Eq.…”

Section: Reaction Of Hoooh With Hoooh (Pathway I) Direct Conversion Tomentioning

confidence: 99%

Section: Summary Of the H2o3 Plus 1 O2 Mechanism (Pathway Ii)mentioning

confidence: 99%

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The gas phase reaction of singlet dioxygen with water: A water-catalyzed mechanism

Muller

Goddard

2002

Proc. Natl. Acad. Sci. U.S.A.

105

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“…15 After Plesnièar a number of theoretical investigations on the HOOOH monomer have been reported on the structures and spectroscopic properties. [16][17][18][19][20] In 2002 Xu and Goddard have proposed the reaction mechanism to form HOOOH from the reaction of HOOH with ozone using quantum mechanical method.…”

mentioning

confidence: 99%

Theoretical Approach for the Structures, Energetics and Spectroscopic Properties of (H₂O₃)_n(n = 1-5) Clusters

Seo¹,

Bahng²,

Kim³

et al. 2012

Bulletin of the Korean Chemical Society

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The geometrical parameters, vibrational frequencies, and binding energies for (H 2 O 3 ) n (n = 1-5) have been investigated using various quantum mechanical techniques. The possible structures of the clusters (n = 2-5) are fully optimized and the binding energies are predicted using energy differences at each optimized geometry. The harmonic vibrational frequencies are also determined and zero-point vibrational energies (ZPVEs) are considered for the better prediction of the binding energy. The best estimation of the binding energy for the dimer is 8.65 kcal/mol. For n = 2 and 3, linear structures with all trans forms of the HOOOH monomers are predicted to be the lowest conformations in energy, while the cyclic structures with all cis-HOOOH monomers are preferable structures for n = 4 and 5.

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Organic tetroxides and mechanism of peroxy radical recombination

Khursan

2014

Patai's Chemistry of Functional Groups

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The chemical properties of organic tetroxides, that is, compounds of a general formula ROOOOR (R = H or organic radical) are discussed. The following tetroxides are considered: hydrogen tetroxide HOOOOH, dialkyl tetroxides ROOOOR, hydrotetroxides ROOOOH, and five‐membered cyclic tetroxides—tetroxolanes. Hydrogen tetroxide is formed via self‐reaction of HOO · radicals on singlet PES; hydroperoxy radical interaction plays an important role in the chemistry of atmosphere. The formation and subsequent decay of tetroxides are discussed in detail. Similar self‐reaction of alkylperoxy radicals leads to organic tetroxides. Its irreversible transformation occurs in two directions depending on the tetroxide structure: the facile homolysis of ROOOOR bond or the induced by αCH bond radical decomposition of tetroxide into hydroperoxy, alkoxy radicals, and carbonyl compound. The latter interaction is the key step in the new mechanism of peroxy radical recombination suggested on the base of extensive analysis of available literature. Hydrotetroxides show properties similar to both HOOOOH and dialkyl tetroxides. A possibility of tetroxolane generation in the reaction of ozone with carbonyl compounds is discussed.

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Kinetics of the reaction between hydroxyl and hydroperoxyl on the singlet potential energy surface

Cited by 54 publications

References 3 publications

The gas phase reaction of singlet dioxygen with water: A water-catalyzed mechanism

The gas phase reaction of singlet dioxygen with water: A water-catalyzed mechanism

Theoretical Approach for the Structures, Energetics and Spectroscopic Properties of (H₂O₃)_n(n = 1-5) Clusters

Organic tetroxides and mechanism of peroxy radical recombination

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Kinetics of the reaction between hydroxyl and hydroperoxyl on the singlet potential energy surface

Cited by 54 publications

References 3 publications

The gas phase reaction of singlet dioxygen with water: A water-catalyzed mechanism

The gas phase reaction of singlet dioxygen with water: A water-catalyzed mechanism

Theoretical Approach for the Structures, Energetics and Spectroscopic Properties of (H2O3)n(n = 1-5) Clusters

Organic tetroxides and mechanism of peroxy radical recombination

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Theoretical Approach for the Structures, Energetics and Spectroscopic Properties of (H₂O₃)_n(n = 1-5) Clusters