Theoretical and thermochemical network approaches to determine the heats of formation for HO2 and its ionic counterparts

Ádám Ganyecz, Jozsef Csontos, Balázs Nagy, M. Kállay

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Abstract

The purpose of this study is to give reliable and accurate thermochemical data for HO2, HO2+, and HO2-. Their heats of formation were determined using quantum chemical calculations with the aid of high-accuracy coupled-cluster 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 δfH0°(HO2) = 14.85 ± 0.22, δfH298°(HO2) = 11.92 ± 0.22, δfH0°(HO2+) = 1110.56 ± 0.40, δfH298°(HO2+) = 1107.64 ± 0.40, δfH0°(HO2-) = -89.04 ± 0. 39, and δfH298°(HO2-) = -91.75 ± 0.39 kJ/mol. In addition, in line with previous accurate data δfH0°(OH) = 37.25 ± 0.03, δfH0°(OH+) = 1293.20 ± 0.03, and δfH0°(H2O2) = 129.48 ± 0.06 kJ/mol were also delivered by our network.

Original languageEnglish
Pages (from-to)1164-1176
Number of pages13
JournalJournal of Physical Chemistry A
Volume119
Issue number7
DOIs
Publication statusPublished - Feb 19 2015

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heat of formation
Born approximation
Born-Oppenheimer approximation
relativistic effects
Enthalpy
enthalpy
scalars
estimates
Hot Temperature
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical and thermochemical network approaches to determine the heats of formation for HO2 and its ionic counterparts. / Ganyecz, Ádám; Csontos, Jozsef; Nagy, Balázs; Kállay, M.

In: Journal of Physical Chemistry A, Vol. 119, No. 7, 19.02.2015, p. 1164-1176.

Research output: Contribution to journalArticle

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abstract = "The purpose of this study is to give reliable and accurate thermochemical data for HO2, HO2+, and HO2-. Their heats of formation were determined using quantum chemical calculations with the aid of high-accuracy coupled-cluster 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 δfH0°(HO2) = 14.85 ± 0.22, δfH298°(HO2) = 11.92 ± 0.22, δfH0°(HO2+) = 1110.56 ± 0.40, δfH298°(HO2+) = 1107.64 ± 0.40, δfH0°(HO2-) = -89.04 ± 0. 39, and δfH298°(HO2-) = -91.75 ± 0.39 kJ/mol. In addition, in line with previous accurate data δfH0°(OH) = 37.25 ± 0.03, δfH0°(OH+) = 1293.20 ± 0.03, and δfH0°(H2O2) = 129.48 ± 0.06 kJ/mol were also delivered by our network.",
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