Noncovalent interactions play an important role for the design of novel drugs, better catalysts, synthesis of complex supramolecular structures, and so on. To develop new materials, a well-founded knowledge of how to control the strength of these interactions is desirable. Despite the many investigations done so far, a quantitative assessment of the intrinsic strength of most types of noncovalent interactions is still missing. Recently and for the first time, the Konkoli-Cremer local modes analysis was successfully used to probe the intrinsic strength of hydrogen and pnicogen bonds. We extended these investigations to more than 300 halogen and chalcogen bonds. A series of electronic effects was found to play a major role for the strength of these noncovalent interactions. Among these are relativistic effects, support by a hydrogen bond, charge transfer, and the formation of 3c-4e bonds. Additionally, a new type of chalcogen bonded complex was found. Based on these effects, new strategies for the design of novel material are suggested. In a subsequent project, a conformationally driven bonding mechanism for a general description of noncovalent interaction involving pnicogen, chalcogen, and halogen atoms was proposed. Apart from noncovalent interactions, we designed a general building principle to explain the stability of small gold clusters based on the σ-aromaticity of Au3 ring subunits. These studies provide an ample view on how the strength of noncovalent interactions can be tuned, serving as a starting point for the rational design of novel materials.
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Oliveira, Vytor, "Quantum Chemical Studies of Noncovalent Interactions and Multicenter Bonds Utilizing Local Vibrational Modes" (2017). Chemistry Theses and Dissertations. 1.