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|Title:||Energetics of the naphthalene/azulene monocation isomerization: density functional and coupled cluster calculations||Authors:||Koster, G.
|Issue Date:||1999||Publisher:||ROYAL SOC CHEMISTRY||Source:||Journal of the Chemical Society: Perkin transactions: 2: physical organic chemistry, (11). p. 2383-2387||Abstract:||The energetics of isomerization between the azulene and naphthalene radical cations have been investigated using the hybrid density functional method B3LYP with the cc-pVDZ basis sets. CCSD/cc-pVDZ energy Calculations were also carried out for selected points along the reaction coordinate. The transition state barrier energies for isomerization are lower than the dissociation limit of C8H6.+' (benzocyclobutadiene(.+)) + C2H2 deduced earlier. A key intermediate is a hydrogen shifted naphthalene isomer analogous to the intermediate suggested in the Dewar-Becker isomerization mechanism for neutral azulene. The norcaradiene isomer of the Dewar-Becker mechanism was found to be a transition structure in the ionic system. Results of the present density functional theory (DFT) and coupled cluster calculations are discussed in the light of recent experimental evidence.||Keywords:||POLYCYCLIC AROMATIC-HYDROCARBONS; DEPENDENT MASS-SPECTRA; THERMAL REARRANGEMENTS; BREAKDOWN GRAPHS; EXACT EXCHANGE; CATIONS||Document URI:||http://hdl.handle.net/1942/5017||ISI #:||000084992600019||Type:||Journal Contribution|
|Appears in Collections:||Research publications|
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