Pd. Pacey et Qtn. Tan, SIMPLE ELECTROSTATIC MODEL FOR THE IONIZATION ENERGIES OF ALKENES, ALKYNES, BROMOALKANES, AND IODOALKANES, Journal of physical chemistry, 99(50), 1995, pp. 17729-17736
It is postulated that the trends in the ionization energies within sev
eral families of organic compounds are caused primarily by the attract
ions between the center of charge in the ion and the induced dipole mo
ments in the alkyl groups of the ion. Simple expressions are developed
for the stabilization energy, which depends on the inverse fourth pow
er of the distance between the charge center and the carbon atoms in t
he alkyl groups. Dipoles induced in the bonds directly attached to the
charged center affect the magnitude of the atomic charge. The mutual
repulsion between induced dipoles in different branches of an isopropy
l or tertbutyl group is also considered. The method allows the calcula
tion of ionization energies by simple arithmetic. There are strong lin
ear relationships between the predictions of the theory and the experi
mental data for 108 alkenes, alkynes, bromoalkanes, and iodoalkanes wi
th linear alkyl chains. The square roots of the mean square deviations
(SRMSD) between the data and the linear relation are between 1.3 and
2.0 kJ mol(-1) (0.013 and 0.021 eV) for each class of compound. These
relationships have also been used to predict ionization energies for 1
8 branched and cyclic compounds, with the resulting SRMSD being 3.4 kJ
mol(-1).