Review of the heat of formation of the hydroperoxyl radical

Shum, Lilian G. S.; Benson, Sidney W.

doi:10.1021/j100241a025

Cited by 59 publications

(22 citation statements)

References 3 publications

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“…In 1983 Shum and Benson 19 Best estimates for Δ f H 298°( HO 2 ). Only those results are shown that claimed better than chemical accuracy; i.e., their associated error bar is less than ±4.2 kJ/mol.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Theoretical and Thermochemical Network Approaches To Determine the Heats of Formation for HO₂ and Its Ionic Counterparts

et al. 2015

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The purpose of this study is to give reliable and accurate thermochemical data for HO 2 , HO 2 + , and HO 2 − . Their heats of formation were determined using quantum chemical calculations with the aid of high-accuracy coupledcluster methods taking account of zero-point vibrational energies, scalar-relativistic effects, and the deficiencies of the Born−Oppenheimer approximation. Furthermore, a thermochemical network, containing 14 experimental and 7 theoretical reaction enthalpies, was set up to determine even more accurate heats of formation. The iteratively reweighted least-squares solution of the network yielded the best heat of formation estimates, which are Δ f H 0°( HO 2 ) = 14.85 ± 0.22, Δ f H 298°( HO 2 ) = 11.92 ± 0.22, Δ f H 0°( HO 2 + ) = 1110.56 ± 0.40, Δ f H 298°( HO 2 + ) = 1107.64 ± 0.40, Δ f H 0°( HO 2 − ) = −89.04 ± 0. 39, and Δ f H 298°( HO 2 − ) = −91.75 ± 0.39 kJ/mol. In addition, in line with previous accurate data Δ f H 0°( OH) = 37.25 ± 0.03, Δ f H 0°( OH + ) = 1293.20 ± 0.03, and Δ f H 0°( H 2 O 2 ) = −129.48 ± 0.06 kJ/mol were also delivered by our network.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Theoretical and Thermochemical Network Approaches To Determine the Heats of Formation for HO₂ and Its Ionic Counterparts

et al. 2015

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“…This result could be explained in terms of the similarity between the bond energies (gas phase) of hydrogen and organic hydroperoxides [11,12].…”

Section: Hydrogen Peroxidementioning

confidence: 89%

Reaction of 2,2?-azinobis (3-ethylbenzothiazoline-6-sulfonic acid (ABTS) derived radicals with hydroperoxides. Kinetics and mechanism

Aliaga

Lissi

1998

Int. J. Chem. Kinet.

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Tert-Butyl hydroperoxide and hydrogen peroxide readily react with the radical cation derived from 2,2Ј-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS). The reaction is inhibited by ABTS and protons, and can be interpreted in terms of a mechanism comprising a partially reversible electron transferؒ followed by the self-reactions of the hydroperoxide derived radicals and reactions between them and another ABTS derived radical. A complete kinetic analysis allows an evaluation of the rate constant for reaction (1). A value of was obtained for both compounds. Ϫ1 Ϫ10.2 M s The back reaction of process (1) is more relevant when tert-butyl hydroperoxide is employed.

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“…Experimental ⌬H f values ranged from 3.5+ 1.0/ −0.5 to 2.940.06 kcal/ mol. 53,[61][62][63][64][65][66][67][68][69] Hardware limitations prevented us from carrying out CCSD͑T͒/aug-cc-pV7Z calculations with the two sets of k functions present on both oxygen atoms. The small contribution from the missing k functions was estimated by performing an exponential extrapolation of the incremental correlation energy lowering associated with each ᐉ value.…”

Section: B Homentioning

confidence: 99%

Probing the limits of accuracy in electronic structure calculations: Is theory capable of results uniformly better than “chemical accuracy”?

Feller

Peterson

2007

The Journal of Chemical Physics

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Current limitations in electronic structure methods are discussed from the perspective of their potential to contribute to inherent uncertainties in predictions of molecular properties, with an emphasis on atomization energies (or heats of formation). The practical difficulties arising from attempts to achieve high accuracy are illustrated via two case studies: the carbon dimer (C2) and the hydroperoxyl radical (HO2). While the HO2 wave function is dominated by a single configuration, the carbon dimer involves considerable multiconfigurational character. In addition to these two molecules, statistical results will be presented for a much larger sample of molecules drawn from the Computational Results Database. The goal of this analysis will be to determine if a combination of coupled cluster theory with large 1-particle basis sets and careful incorporation of several computationally expensive smaller corrections can yield uniform agreement with experiment to better than "chemical accuracy" (+/-1 kcal/mol). In the case of HO2, the best current theoretical estimate of the zero-point-inclusive, spin-orbit corrected atomization energy (SigmaD0=166.0+/-0.3 kcal/mol) and the most recent Active Thermochemical Table (ATcT) value (165.97+/-0.06 kcal/mol) are in excellent agreement. For C2 the agreement is only slightly poorer, with theory (D0=143.7+/-0.3 kcal/mol) almost encompassing the most recent ATcT value (144.03+/-0.13 kcal/mol). For a larger collection of 68 molecules, a mean absolute deviation of 0.3 kcal/mol was found. The same high level of theory that produces good agreement for atomization energies also appears capable of predicting bond lengths to an accuracy of +/-0.001 A.

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Review of the heat of formation of the hydroperoxyl radical

Abstract: The currently reported values of the heat of formation of hydroperoxyl radical have been reviewed. A best value, Mff°(H02) = 3.5^5°kcal/mol, is recommended.

Cited by 59 publications

References 3 publications

Theoretical and Thermochemical Network Approaches To Determine the Heats of Formation for HO₂ and Its Ionic Counterparts

Theoretical and Thermochemical Network Approaches To Determine the Heats of Formation for HO₂ and Its Ionic Counterparts

Reaction of 2,2?-azinobis (3-ethylbenzothiazoline-6-sulfonic acid (ABTS) derived radicals with hydroperoxides. Kinetics and mechanism

Probing the limits of accuracy in electronic structure calculations: Is theory capable of results uniformly better than “chemical accuracy”?

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Review of the heat of formation of the hydroperoxyl radical

Abstract: The currently reported values of the heat of formation of hydroperoxyl radical have been reviewed. A best value, Mff°(H02) = 3.5^5°kcal/mol, is recommended.

Cited by 59 publications

References 3 publications

Theoretical and Thermochemical Network Approaches To Determine the Heats of Formation for HO2 and Its Ionic Counterparts

Theoretical and Thermochemical Network Approaches To Determine the Heats of Formation for HO2 and Its Ionic Counterparts

Reaction of 2,2?-azinobis (3-ethylbenzothiazoline-6-sulfonic acid (ABTS) derived radicals with hydroperoxides. Kinetics and mechanism

Probing the limits of accuracy in electronic structure calculations: Is theory capable of results uniformly better than “chemical accuracy”?

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Theoretical and Thermochemical Network Approaches To Determine the Heats of Formation for HO₂ and Its Ionic Counterparts

Theoretical and Thermochemical Network Approaches To Determine the Heats of Formation for HO₂ and Its Ionic Counterparts