Comparison of G3 and G4 Theories for Radical Addition and Abstraction Reactions
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Lin, Ching-Yeh; Hodgson, Jennifer; Namazian, Mansoor; Coote, Michelle
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A test set of 21 radical addition and 28 hydrogen abstraction reactions has been studied at the Wl, G4, G3X, G3X(MP2), and G3X(MP2)-RAD levels of theory with a view to establishing whether the recently introduced G4 theory offers improved performance over the G3 methods. All methods tested approximated the benchmark Wl values to within a mean absolute deviation (MAD) of 4 kJ mol -1 or less, although maximum absolute deviations for problematic reactions (such as radical addition to thiocarbonyl...[Show more]
dc.contributor.author | Lin, Ching-Yeh | |
---|---|---|
dc.contributor.author | Hodgson, Jennifer | |
dc.contributor.author | Namazian, Mansoor | |
dc.contributor.author | Coote, Michelle | |
dc.date.accessioned | 2015-12-10T22:32:55Z | |
dc.identifier.issn | 1089-5639 | |
dc.identifier.uri | http://hdl.handle.net/1885/55995 | |
dc.description.abstract | A test set of 21 radical addition and 28 hydrogen abstraction reactions has been studied at the Wl, G4, G3X, G3X(MP2), and G3X(MP2)-RAD levels of theory with a view to establishing whether the recently introduced G4 theory offers improved performance over the G3 methods. All methods tested approximated the benchmark Wl values to within a mean absolute deviation (MAD) of 4 kJ mol -1 or less, although maximum absolute deviations for problematic reactions (such as radical addition to thiocarbonyl compounds) can be as much as 10 kJ mol-1 for the G3 methods. The new noncanceling higher-level correction (HLC) term in G4 was found to be capable of mitigating these errors in radical addition, but it introduced a systematic error to the reaction energies of the abstraction reactions, and its format may therefore require re-examination. G3 methods were shown to offer "chemical accuracy" even for these problematic cases, provided they were corrected to the Wl level of theory via an ONIOM-based approach. | |
dc.publisher | American Chemical Society | |
dc.source | Journal of Physical Chemistry A | |
dc.subject | Keywords: Absolute deviations; Abstraction reactions; Hydrogen abstraction reactions; Mean absolute deviations; Radical additions; Reaction energies; Test sets; Thiocarbonyl compounds; Abstracting; Error correction; Hydrogen; Systematic errors; Addition reactions | |
dc.title | Comparison of G3 and G4 Theories for Radical Addition and Abstraction Reactions | |
dc.type | Journal article | |
local.description.notes | Imported from ARIES | |
local.identifier.citationvolume | 113 | |
dc.date.issued | 2009 | |
local.identifier.absfor | 030799 - Theoretical and Computational Chemistry not elsewhere classified | |
local.identifier.absfor | 030399 - Macromolecular and Materials Chemistry not elsewhere classified | |
local.identifier.ariespublication | u4217927xPUB347 | |
local.type.status | Published Version | |
local.contributor.affiliation | Lin, Ching-Yeh, College of Physical and Mathematical Sciences, ANU | |
local.contributor.affiliation | Hodgson, Jennifer, College of Physical and Mathematical Sciences, ANU | |
local.contributor.affiliation | Namazian, Mansoor, College of Physical and Mathematical Sciences, ANU | |
local.contributor.affiliation | Coote, Michelle, College of Physical and Mathematical Sciences, ANU | |
local.description.embargo | 2037-12-31 | |
local.bibliographicCitation.issue | 15 | |
local.bibliographicCitation.startpage | 3690 | |
local.bibliographicCitation.lastpage | 3697 | |
local.identifier.doi | 10.1021/jp900649j | |
local.identifier.absseo | 970103 - Expanding Knowledge in the Chemical Sciences | |
dc.date.updated | 2016-02-24T10:42:38Z | |
local.identifier.scopusID | 2-s2.0-64849090861 | |
local.identifier.thomsonID | 000265030400037 | |
Collections | ANU Research Publications |
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