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Electron Delocalization Range in Atoms and on Molecular Surfaces

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journal contribution
posted on 10.06.2016, 19:18 by Benjamin G. Janesko, Kenneth B. Wiberg, Giovanni Scalmani, Michael J. Frisch
The electron delocalization range function EDR­(r⃗; d) (J. Chem. Phys. 2014, 141, 144104) quantifies the extent to which an electron at point r⃗ in a calculated wave function delocalizes over distance d. This work illustrates how atomic averages of the EDR, and plots of the EDR on molecule surfaces, provide a chemically intuitive picture of the sizes of occupied orbital lobes in different regions. We show how the surface and atomic delocalization distinguish aminophosphine ligand’s hard N and soft P lone pairs, distinguish the site preference for Ag+ cation binding to conjugated oligomers, and provide information that is different from and complementary to conjugation lengths. Applications to strong correlation and the prototropic tautomerization of phosphinylidenes R1R2HPO illustrates how the surface and atomic delocalization can work with other tools to provide a nuanced picture of reactivity.