Substituent effect in 1-X-decanes and 3-X-gonanes based on core-electron binding energies calculated with density-functional theory

Abstract

The substituent effect in substituted n-decanes (1-X-decan), chain σ-systems of saturated hydrocarbon, and C3 substituted gonanes (3-X-gonane), fused ring σ-systems, where X=H, NO2, CHO, F, CH3, But (tertiary butyl), was investigated using calculated core electron binding energies. The energies were calculated using the density-functional theory (DFT) with the Perdew–Wang 1986 exchange and the Perdew–Wang 1991 correlation functionals. A triple-zeta polarized Slater type basis set was employed. The effect of the electron withdrawing substituents, NO2, F, and CHO, is felt all the way to the end of the 10-carbon chain in 1-X-decane. Similarly, the effect of the electron withdrawing substituents is felt to the D ring carbons in 3-X-gonane. A possible explanation of the long-range effect is given. It was shown that the substituent effect was very similar, but not identical, in 1-X-decane and 3-X-gonane in quality and quantity.