AI Article Synopsis
- The ground states of unsaturated molecules with C(s) symmetry allow for distinct calculations of σ and π molecular orbitals, enabling detailed structural analysis.
- Various compounds, including vinyl derivatives and six-membered ring heterocycles, were studied, with results displayed as plots reflecting changes in population across different atoms.
- The interaction between electron-withdrawing groups and alkene carbons leads to significant σ and π density transfer, resembling behaviors seen in metal complexes with carbonyls or other ligands.
Article Abstract
The ground states of unsaturated molecules with C(s) symmetry have separate σ and π molecular orbitals. This makes it possible to separately calculate the σ and π Hirshfeld populations and to analyze the effect of structural changes in more detail. A number of types of compounds have been studied: vinyl derivatives, 1-substituted hexatrienes, phenyl derivatives, and six-membered ring heterocycles. The results are shown as plots of changes in population vs atoms. The σ and π components vary widely, depending on π conjugation, σ inductive effects, and σ/π polarization. When an electron withdrawing group is attached to an alkene carbon, significant σ density is transferred to it, and to compensate π density is transferred to the substituent. Such interactions are similar to those found when a carbonyl or other ligands are attached to a metal.
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| http://dx.doi.org/10.1021/acs.jctc.5b01149 | DOI Listing |
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