An Ab Initio Study of the Reaction Mechanism of Co++NH3

dc.contributor.author Taketsugu, Tetsuya
dc.contributor.author Gordon, Mark
dc.contributor.author Gordon, Mark
dc.contributor.department Ames Laboratory
dc.contributor.department Chemistry
dc.date 2018-02-17T07:48:07.000
dc.date.accessioned 2020-06-30T01:19:16Z
dc.date.available 2020-06-30T01:19:16Z
dc.date.copyright Wed Jan 01 00:00:00 UTC 1997
dc.date.issued 1997-05-01
dc.description.abstract <p>To investigate the mechanism for N–H bond activation by a transition metal, the reactions of Co+(3F,5F) with NH3 have been studied with complete active space self-consistent field (CASSCF), multireference configuration interaction (MR-SDCI), and multireference many body perturbation theory (MRMP) wave functions, using both effective core potential and all-electron methods. Upon their initial approach, the reactants yield an ion–molecule complex, CoNH+3(3E,5A2,5A1), with retention of C3ν symmetry. The Co+=NH3 binding energies are estimated to be 49 (triplet) and 45 (quintet) kcal/mol. Subsequently, the N–H bond is activated, leading to an intermediate complex H–Co–NH+2 (C2ν symmetry), through a three-center transition state with an energy barrier of 56–60 (triplet) and 70–73 (quintet) kcal/mol. The energy of H–Co–NH+2, relative to that of CoNH+3, is estimated to be 60 to 61 (triplet) and 44 (quintet) kcal/mol. However, the highest levels of theory employed here (including dynamic correlation corrections) suggest that the triplet intermediate HCoNH+2 may not exist as a minimum on the potential energy surface. Following Co–N or H–Co bond cleavage, the complexH–Co–NH+2 leads to HCo++NH2 or H+CoNH+2. Both channels (triplet and quintet) are found to be endothermic by 54–64 kcal/mol.</p>
dc.description.comments <p>The following article appeared in <em>Journal of Chemical Physics</em> 106 (1997): 8504, and may be found at doi:<a href="http://dx.doi.org/10.1063/1.474058" target="_blank">10.1063/1.474058</a>.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/chem_pubs/319/
dc.identifier.articleid 1317
dc.identifier.contextkey 7922677
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/319
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/14767
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/319/1997_Gordon_AbInitioCo_.pdf|||Fri Jan 14 23:32:56 UTC 2022
dc.source.uri 10.1063/1.474058
dc.subject.disciplines Chemistry
dc.subject.keywords Reaction mechanisms
dc.subject.keywords Activation energies
dc.subject.keywords Chemical reaction theory
dc.subject.keywords Configuration interaction
dc.subject.keywords Many body problems
dc.title An Ab Initio Study of the Reaction Mechanism of Co++NH3
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication 1a5927c0-5a5f-440e-86e0-9da8dc6afda0
relation.isOrgUnitOfPublication 25913818-6714-4be5-89a6-f70c8facdf7e
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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