Effect of free valence on the characteristics of internal rotation in n-alkyl radicals

Abstract

A study of internal rotation in the radicals n-CnH2n+1C·H2, (2 ≤ n ≤ 7) was carried out for the case of rotation around the bonds not including the radical center. 21 potential functions of internal rotation V(φ) were calculated. The coefficients in V(φ) were shown to depend only on the immediate environment at the bond of rotation. Characteristics of internal rotation in n-alkyl radicals were compared with related parameters of the corresponding alkane molecules. The generalized function Vav(φ) with the coefficients defined only by the position of the bond of rotation in the hydrocarbon chain and possessing the transposition property were proposed. The functions Vav(φ) were recommended for the simulation of the structure and properties of large molecules containing hydrocarbon fragments. This work continues a systematic study on the characteristics of the internal rotation in the n-alkane molecules and the groups containing free valence in n-alkyl radicals.