Connection between nuclear and electronic Fukui functions beyond frontier molecular orbitals

Based on the relationship between average local ionization energy I(r) and average local electron affinity A(r) with the electronic Fukui functions, i.e., f(-)(r) and f(+)(r), respectively, in this paper, we establish a connection between nuclear and electronic Fukui functions beyond frontier molecular orbitals. As a consequence of this connection, we obtain expressions of average nuclear Fukui functions interpreted as a variation of average nucleophilicity or electrophilicity (weighted by the electronic orbital Fukui functions) with respect to nuclear displacements, which goes beyond the highest occupied molecular orbital/or lowest unoccupied molecular orbital consideration. Furthermore, from this connection and considering the frontier molecular orbital approximation, we derive expressions of nuclear Fukui functions in terms of the atom-condensed electronic Fukui functions, which imply a locality in the chemical reactivity and could be used to study the variation of local nucleophilicity or electrophilicity with respect to nuclear displacements. Finally, this new way to interpret the nuclear Fukui function could be useful in the future to study the chemical reactivity related to molecular vibrations, internal rotations, bond dissociation, chemical reaction along the model of reaction coordinate, and so on.

Automated summary

In this paper, we establish a connection between the average local ionization energy, electron affinity, and electronic Fukui functions, and derive expressions for nuclear Fukui functions beyond the highest occupied molecular orbital/lowest unoccupied molecular orbital approximation. This provides a new way to interpret and study the variation of local nucleophilicity or electrophilicity with respect to nuclear displacements, and has potential applications in molecular vibrations, internal rotations, bond dissociation, and chemical reactions.