Internal rotation in mononitro-n-alkyl radicals

Internal rotation in the C·H₂(CH₂) _n NO₂ (n ≤ 7) type radicals has been studied. 44 potential functions of the internal rotation, V(φ), have been calculated taking advantage of the B3LYP/6-311++(3df,3pd) and MP2/6-311++(3df,3pd) methods. The trends observed in the series of parameters characterizing the internal rotation have been explained in view of the electron clouds conjugation, the inductive effect of the end groups, the gauche effect, and the rotation tops interaction. The coefficients of V(φ) have been shown to depend predominantly on the nearest surrounding of the rotation axis. Based on this, the generalized functions, V _av(φ), have been developed, their coefficients being dependent exclusively on the rotating bond position. Such functions are convenient for molecular modeling applications.