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An Electric Field–Based Approach for Quantifying Volumes and Radii of Chemically Affected Space

Chemical shape and size play a critical role in chemistry. The van der Waal (vdW) radii, a familiar manifold used to quantify size by assuming overlapping spheres, provides rapid estimates of size in atoms, molecules, and materials. However, the vdW method may be too rigid to describe highly polarized systems and chemical systems that stray from spherical atomistic environments. To deal with these exotic chemistries, numerous alternate methods based on electron density have been presented. While each boasts inherent generality, all define the size of a chemical system, in one way or another, by its electron density. Herein, we revisit the timeless problem of assessing sizes of atoms and molecules, instead through examination of the electric field produced by them. While conceptually different than nuclei-centered methods like that of van der Waal, the field assesses chemically affected volumes. This approac