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@ARTICLE{Baric:51224,
      author       = {Baric, D. and Kovacevic, B. and Maksic, Z. B. and Müller,
                      T.},
      title        = {{A} {N}ovel {A}pproach in {A}nalyzing {A}romaticity by
                      {H}omo- and {I}sostructural {R}eactions: {A}n ab {I}nitio
                      {S}tudy of {F}luorobenzenes},
      journal      = {The journal of physical chemistry / A},
      volume       = {109},
      issn         = {1089-5639},
      address      = {Washington, DC},
      publisher    = {Soc.},
      reportid     = {PreJuSER-51224},
      pages        = {10594},
      year         = {2005},
      note         = {Record converted from VDB: 12.11.2012},
      abstract     = {The influence of fluorine substitutions on the stability of
                      benzene is examined by using the Hartree-Fock (HF) and MP2
                      models. It is conclusively demonstrated that homodesmotic
                      reactions based on the open-chain zigzag polyenes are
                      unsatisfactory. A comparison of the intramolecular
                      interactions of educts and products shows that they are not
                      well balanced. Hence, these reactions should be abandoned in
                      discussing aromaticity. A much better vehicle for exploring
                      aromaticity is provided by homostructural reactions, which
                      employ cyclic monoene and diene as reference model
                      compounds. Their heavy atoms are enforced to assume planar
                      geometries to enable sigma/pi separation. The HF/cc-pVTZ
                      calculations show that extrinsic aromaticity of benzene B
                      DeltaE(ease)(B)() arises both from the sigma- and
                      pi-contributions. They are -14.8 and -23.1 in kcal/mol,
                      respectively, if the stockholder energy partitioning scheme
                      is employed. This result implies that both the sigma- and
                      pi-frameworks contribute to the aromatic stabilization of B,
                      the latter being more important. The total aromatic
                      stabilization DeltaE(ease)(B)() is -37.9 kcal/mol.
                      Schleyer's indene-isoindene isomerization approach also
                      strongly indicates that the decisive factor in determining
                      the aromatic stability of the benzene moiety is the
                      pi-electron framework. The origin of extrinsic aromaticity
                      is identified as the increased nuclear-electron attraction
                      of both sigma- and pi-electrons, if 1,3-cyclohexadiene is
                      used as a gauge compound. Further, by using a system of
                      isostructural reactions, it is conclusively demonstrated
                      that fluorobenzenes exhibit a remarkable additivity of the
                      substituent effects, as far as the stability of multiply
                      substituted benzenes is concerned. This additivity rule is
                      so accurate that it enables delineation of the fluorine
                      repulsions and the aromaticity defect DeltaE(AD). It appears
                      that the DeltaE(AD) values increase upon sequential fluorine
                      substitution at the next nearest (vicinal) position thus
                      making multiply fluorinated benzenes less stable.},
      keywords     = {Butadienes: chemistry / Chemistry, Physical / Ethylenes:
                      chemistry / Fluorobenzenes: chemistry / Hydrocarbons,
                      Aromatic: chemistry / Hydrocarbons, Cyclic: chemistry /
                      Hydrocarbons, Fluorinated: chemistry / Models, Chemical /
                      Molecular Structure / Physicochemical Phenomena / Butadienes
                      (NLM Chemicals) / Ethylenes (NLM Chemicals) / Fluorobenzenes
                      (NLM Chemicals) / Hydrocarbons, Aromatic (NLM Chemicals) /
                      Hydrocarbons, Cyclic (NLM Chemicals) / Hydrocarbons,
                      Fluorinated (NLM Chemicals) / 1,3-butadiene (NLM Chemicals)
                      / ethylene (NLM Chemicals) / J (WoSType)},
      cin          = {ZAM},
      ddc          = {530},
      cid          = {I:(DE-Juel1)VDB62},
      pnm          = {Betrieb und Weiterentwicklung des Höchstleistungsrechners},
      pid          = {G:(DE-Juel1)FUEK254},
      shelfmark    = {Chemistry, Physical / Physics, Atomic, Molecular $\&$
                      Chemical},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {pmid:16834316},
      UT           = {WOS:000233436900016},
      doi          = {10.1021/jp0532871},
      url          = {https://juser.fz-juelich.de/record/51224},
}