Fable Theory & Computation LLC, Washington, DC 20009, USA.
J Phys Chem A. 2012 Aug 23;116(33):8644-52. doi: 10.1021/jp3053604. Epub 2012 Aug 10.
We have investigated the use of the average local ionization energy, Icombining overline(r), as a means for rapidly predicting the relative reactivities of different sites on two model graphene surfaces toward the successive addition of one, two, and three hydrogen or fluorine atoms. The Icombining overline(r) results were compared with directly computed interaction energies, at the B3LYP/6-311G(d,p) level. Icombining overline(r) correctly predicts that the edges of graphene sheets are more reactive than the interior portions. It shows that added hydrogens activate the adjoining (ortho) sites and deactivate those that are separated by one site (meta). Overall, Icombining overline(r) is effective for rapidly (single calculations) estimating the relative site reactivities of these large systems, although it reflects only the system prior to an interaction and cannot take into account postinteraction factors, e.g., structural distortion.
