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000042310 0247_ $$2DOI$$a10.1002/cphc.200400061
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000042310 084__ $$2WoS$$aChemistry, Physical
000042310 084__ $$2WoS$$aPhysics, Atomic, Molecular & Chemical
000042310 1001_ $$0P:(DE-HGF)0$$aKovacevic, B.$$b0
000042310 245__ $$aThe Origin of Aromaticity: Important Role of the Sigma Framework in Benzene
000042310 260__ $$aWeinheim$$bWiley-VCH Verl.$$c2004
000042310 300__ $$a1352 - 1364
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000042310 440_0 $$010582$$aChemPhysChem$$v5$$x1439-4235$$y9
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000042310 520__ $$aThe physical nature of aromaticity is addressed at a high ab initio level. It is conclusively shown that the extrinsic aromatic stabilization energy of benzene E(ease)B, estimated relative to its linear polyene counterpart(s), is very well-reproduced at the Hartree-Fock (HF) level. This is a consequence of the fact that the contributions arising from the zero-point vibrational energy (ZPVE) and electron correlation are rather small. More specifically, they yield together 2.0 kcalmol(-1) to the destabilization of benzene. A careful scrutiny of the HF energies by virial theorem shows further that the kinetic energies of the sigma and pi electrons E(T)HF(sigma) and E(T)HF(pi) are strictly additive in the gauge linear zig-zag polyenes, which also holds for their sum Et(T)HF This finding has the important corollary that E(ease)B is little dependent on the choice of the homodesmic reactions involving zig-zag polyenes. A detailed physical analysis of the sigma- and pi-electron contributions to extrinsic aromaticity requires explicit introduction of the potential energy terms Vne, Vee, and Vnn, which signify Coulomb interactions between the electrons and the nuclei. The Vee term involves repulsive interaction Vee(sigmapi) between the sigma and pi electrons, which cannot be unequivocally resolved into sigma and pi contributions. The same holds for the Vnn energy, which implicitly depends on the electron density distribution via the Born-Oppenheimer (BO) potential energy surface. Several possibilities for partitioning Vee(sigmapi) and Vnn terms into sigma and pi components are examined. It is argued that the stockholder principle is the most realistic, which strongly indicates that E(ease)B is a result of favorable sigma-framework interactions. In contrast, the pi-electron framework prefers the open-chain linear polyenes.
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000042310 65320 $$2Author$$aab initio calculations
000042310 65320 $$2Author$$aaromaticity
000042310 65320 $$2Author$$aquantum chemistry
000042310 65320 $$2Author$$avirial theorem
000042310 7001_ $$0P:(DE-HGF)0$$aBaric, D.$$b1
000042310 7001_ $$0P:(DE-HGF)0$$aMaksic, Z.$$b2
000042310 7001_ $$0P:(DE-Juel1)132204$$aMüller, T.$$b3$$uFZJ
000042310 773__ $$0PERI:(DE-600)2025223-7$$a10.1002/cphc.200400061$$gVol. 5, p. 1352 - 1364$$p1352 - 1364$$q5<1352 - 1364$$tChemPhysChem$$v5$$x1439-4235$$y2004
000042310 8567_ $$uhttp://dx.doi.org/10.1002/cphc.200400061
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000042310 9141_ $$y2004
000042310 915__ $$0StatID:(DE-HGF)0010$$aJCR/ISI refereed
000042310 9201_ $$0I:(DE-Juel1)VDB62$$d31.12.2007$$gZAM$$kZAM$$lZentralinstitut für Angewandte Mathematik$$x0
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