Computational analysis of the through-bond interactions of electronegative atoms

CHED 961

Taylor Arnold Barnes, and Preston J. MacDougall, Department of Chemistry, Middle Tennessee State University, Murfreesboro, TN 37132
The manner in which strongly electronegative atoms interact through bonds is a question of great significance in the field of conformational analysis. This study examines the conformational importance of induced through-bond shifts in electron density caused by electron-withdrawing groups. Quantum chemical calculations are used to determine the difference in energy between the conformations of a variety of species in which a terminal halogen is separated from an electron-withdrawing group by a chain of at least four carbons. This makes it possible to estimate the contribution of the through-bond interaction energies to the relative stabilities of the conformations. In order to develop a model for understanding the nature of these interactions, the through-bond molecular interaction energies of each compound will be compared to the corresponding changes in the atomic properties of the halogen, which are computed using the Quantum Theory of Atoms in Molecules (QTAIM).