Effect of free valence on the electronic structure of n-alcohol radicals

Abstract

The paper presents the results of a study of the effect of free valence (when a hydrogen atom is separated) on the electronic structure of n-alcohol radicals by the example of radicals of n-heptanol derivatives (C●H2-(CH2)6OH, CH3-C●H-(CH2)5OH, C2H5-C●H-(CH2)4OH, C3H7-C●H-(CH2)3OH, C4H9-C●H-(CH2)2OH, C5H11-C●H-CH2OH, C6H13-C●H-OH, C7H15-O●). Geometry optimization and the electron density distribution in these compounds was obtained by the density functional method B3LYP/6-311++G(3df,3pd) 6d 10f. The electronic structure of the selected molecules and radicals was investigated within the framework of the «quantum theory of atoms in a molecule» (QTAIM): the electronic parameters of atoms and atomic groups were calculated, the spin density distribution was studied, the concepts of «radical center» and «free valence» were quantitatively characterized. The inductive effect and the tolerability of atomic groups are considered, and a qualitative scale of group electronegatives is compiled. The disturbing effect of various atomic groups, including those containing free valence, on the hydrocarbon chain is compared by comparing the integral parameters of the groups included in the compounds under study with the parameters of the «standard» groups.

Keywords

• quantum theory of atoms in molecules
• electron density
• electronegativity
• inductive effect
• free valence
• radical center