Accurate Benchmark Calculation of the Reaction Barrier Height for Hydrogen Abstraction by the Hydroperoxyl Radical from Methane. Implications for CnH2n+2 where n = 2 → 4

4, the reactions are investigated at the CCSD(T) level in the correlation-consistent triple-zeta (cc-pVTZ) basis. The results are adjusted to the benchmark methane reaction and compared with those from other approaches that are commonly used in the field such as CBS-QB3, CBS-APNO, and density functional theory. Rate constants are computed in the framework of transition state theory, and the results are compared with previous values available. -->

ISSN:	1520-5215 1089-5639
DOI:	10.1021/jp8012464
Přístupová URL adresa:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::3521db40dd40f4ef31d6158a3b4945bb https://doi.org/10.1021/jp8012464
Přírůstkové číslo:	edsair.doi.dedup.....3521db40dd40f4ef31d6158a3b4945bb
Autor:	John M. Simmie, Wim Klopper, Henry J. Curran, Jorge Aguilera-Iparraguirre
Rok vydání:	2008
Předmět:	Transition state theory chemistry.chemical_compound Reaction rate constant Hydroperoxyl Field (physics) Computational chemistry Chemistry Thermodynamics Density functional theory Limit (mathematics) Physical and Theoretical Chemistry Hydrogen atom abstraction Methane
Zdroj:	The Journal of Physical Chemistry A. 112:7047-7054
ISSN:	1520-5215 1089-5639
DOI:	10.1021/jp8012464
Popis:	The CH4 + HO2(*) reaction is studied by using explicitly correlated coupled-cluster theory with singles and doubles (CCSD-R12) in a large 19s14p8d6f4g3h basis (9s6p4d3f for H) to approach the basis-set limit at the coupled-cluster singles-doubles level. A correction for connected triple excitations is obtained from the conventional CCSD(T) coupled-cluster approach in the correlation-consistent quintuple-zeta basis (cc-pV5Z). The highly accurate results for the methane reaction are used to calibrate the calculations of the hydroperoxyl-radical hydrogen abstraction from other alkanes. For the alkanes C(n)H(2n+2) with n = 2 --> 4, the reactions are investigated at the CCSD(T) level in the correlation-consistent triple-zeta (cc-pVTZ) basis. The results are adjusted to the benchmark methane reaction and compared with those from other approaches that are commonly used in the field such as CBS-QB3, CBS-APNO, and density functional theory. Rate constants are computed in the framework of transition state theory, and the results are compared with previous values available.
Databáze:	OpenAIRE
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