The quantum theory of atoms in molecules (QTAIM) is a powerful method for recovering chemical properties. QTAIM partitions the electron charge density (ρ) into volumes of space that correspond to each atom in a molecule. Each atom (or atomic basin) is bounded by zero-flux-surfaces (ZFSs) in the gradient of ρ, allowing for the calculation of atomic properties including charges, condensed Fukui functions, and energies. Atom condensed Fukui functions can be used to predict which atom in a molecule is most likely to undergo electrophilic or nucleophilic attack. Atomic basins can be further decomposed into gradient bundles – volumes bounded by ZFSs within atomic basins – that can be used to create a higher resolution picture of reactivity. This talk will explore gradient bundle condensed Fukui functions, which provide higher accuracy information on the most probable sites for reactions to occur <i>within</i> each atom. Furthermore, external electric fields (EEFs) can be applied experimentally to control stereospecificity due to the interaction of EEFs with ρ. The exact changes in ρ that occur due to EEFs can be quantified computationally using gradient bundle condensed Fukui functions.

Extensions to QTAIM: Predicting reactivity using gradient bundles

ACS Spring 2022

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