Conformation and Bonding: Theoretical Studies on Conformational Effects and Lewis Pair Stability

This thesis consists of a collection of density functional theory investigations on conformational effects and bonding mechanism in halogenated model systems. First, thorough analyses of the physical forces underlying the gauche effect and the rotational barriers of 1,2-disubstituted ethanes have been performed. Then, the trends in bond strength of archetypal donor–acceptor Lewis pairs have been systematically evaluated. The main purpose is to obtain physically meaningful rationales to explain the studied chemical phenomena. The detailed analyses presented herein shed light on often overlooked quantum chemical effects behind the observed conformational preferences and bonding strengths. It is expected that the fundamental insights provided in this thesis will be a step towards a more comprehensive understanding of the effect of halogen atoms on the structure and bonding of organic and inorganic compounds, which could be extended to rationalize, predict, and tune the properties of more complex molecular systems.