It is common to use the electron density to partition a system into atomic regions. The necessity for such a partitioning scheme is rooted in the unquestionable role of atoms in chemistry. Nevertheless, atomic properties are not well-defined concepts within the domain of quantum mechanics, as they are not physical observables. One of the most popular families of atoms-in-molecules models is the Hirshfeld partitioning schemes. They produce fuzzy atomic boundaries by distributing the molecular electron density at each point between all the constituent nuclear centers. The various flavors of the Hirshfeld scheme differ mainly in how the reference promolecular density is defined.<br/>We have established the pervasiveness of the Hirshfeld portioning by extending its information-theoretic framework. This characterizes the family of f-divergence measures as necessary and sufficient for deriving Hirshfeld scheme. Then, we have developed a variational version of Hirshfeld partitioning method, called Additive Variational Hirshfeld (AVH). The key idea is finding the promolecular density, expanded as a linear combination of charged and neutral spherically-averaged isolated atomic densities in their ground and/or excited states, that resembles the molecular density as much as possible. Using Kullback-Liebler divergence measure, this automatically guarantees that each atom and proatom have the same number of electrons and that the partitioning is size consistent. The robustness of this method is confirmed by testing it on various datasets. Considering the mathematical properties and our numerical results, we believe that AVH has the potential to supplant other Hirshfeld partitioning schemes in future.

Variational information-theoretic atoms-in-molecules

255th National Meeting (2018)

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