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Molecular Physics
An International Journal at the Interface Between Chemistry and Physics
Volume 107, 2009 - Issue 8-12: A Special Issue in Honour of Professor Henry F. Schaefer
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Invited Articles

On the aromatic stabilization energy of the 4N π electron pyrene

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Pages 1177-1186 | Received 05 Nov 2008, Accepted 28 Jan 2009, Published online: 07 Oct 2010

References

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  • The 4 kcal/mol correction for each Csp 2-Csp 2/Csp 3-Csp 3 imbalance is derived from the experimental BSRE value (14.7 ± 0.6 kcal/mol) and the BLW computed PWRE (15.3 kcal/mol, at the higher B3LYP/6-311+G** level) value given for trans-butadiene. Both methods give essentially the same numerical results within the experimental error. Note that for all BSRE equations, there is always twice as much Csp 2-H/Csp 3-H mismatches compared to the Csp 2-Csp 2/Csp 3-Csp 3 imbalances. For butadiene, there are two Csp 2-H favoring the left side of the equation, but one extra Csp 2-Csp 2 favoring the right side. Thus, by taking 2 kcal/mol for each Csp 2-H/Csp 3-H imbalance 31, the correction for each Csp 2-Csp 2/Csp 3-Csp 3 mismatch is ca 4 kcal/mol. Notably, no hybridization imbalance corrections are needed for BSRE equations
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  • The BLW computed PWRE of the D 2 biphenyl (130.8 kcal/mol) is less than its D 2 h form (133.0 kcal/mol). This is due to the greater interaction between the two co-planar benzene rings of the latter. Similarly, the PWRE of a hypothetical butadiene resembling the bridging butadiene subunit in the D 2 biphenyl (9.0 kcal/mol, 41.4 deg dihedral angle) is less than that of syn butadiene (10.7 kcal/mol, 0 deg dihedral angle). The PWRE of the D 2 biphenyl can only be derived indirectly, due to the orthogonality constraints of applying the BLW method

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