Atoms in molecules in real space: a fertile field for chemical bonding
Por:
Martin Pendas, Angel, Francisco, Evelio, Suarez, Dimas, Costales, Aurora, Diaz, Natalia, Munarriz, Julen, Rocha-Rinza, Tomas, Guevara-Vela, Jose Manuel
Publicada:
12 abr 2023
Ahead of Print:
1 mar 2023
Resumen:
In this perspective, we review some recent advances in the concept of
atoms-in-molecules from a real space perspective. We first introduce the
general formalism of atomic weight factors that allows unifying the
treatment of fuzzy and non-fuzzy decompositions under a common algebraic
umbrella. We then show how the use of reduced density matrices and their
cumulants allows partitioning any quantum mechanical observable into
atomic or group contributions. This circumstance provides access to
electron counting as well as energy partitioning, on the same footing.
We focus on how the fluctuations of atomic populations, as measured by
the statistical cumulants of the electron distribution functions, are
related to general multi-center bonding descriptors. Then we turn our
attention to the interacting quantum atom energy partitioning, which is
briefly reviewed since several general accounts on it have already
appeared in the literature. More attention is paid to recent
applications to large systems. Finally, we consider how a common
formalism to extract electron counts and energies can be used to
establish an algebraic justification for the extensively used bond
order-bond energy relationships. We also briefly review a path to
recover one-electron functions from real space partitions. Although most
of the applications considered will be restricted to real space atoms
taken from the quantum theory of atoms in molecules, arguably the most
successful of all the atomic partitions devised so far, all the
take-home messages from this perspective are generalizable to any real
space decompositions.
Filiaciones:
Martin Pendas, Angel:
Univ Oviedo, Dept Quim Fis & Analit, Oviedo 33006, Spain
Francisco, Evelio:
Univ Oviedo, Dept Quim Fis & Analit, Oviedo 33006, Spain
Suarez, Dimas:
Univ Oviedo, Dept Quim Fis & Analit, Oviedo 33006, Spain
Costales, Aurora:
Univ Oviedo, Dept Quim Fis & Analit, Oviedo 33006, Spain
Diaz, Natalia:
Univ Oviedo, Dept Quim Fis & Analit, Oviedo 33006, Spain
Munarriz, Julen:
Univ Oviedo, Dept Quim Fis & Analit, Oviedo 33006, Spain
Rocha-Rinza, Tomas:
Univ Nacl Autonoma Mexico, Inst Quim, Circuito Exterior,Ciudad Univ,Delegac Coyoacan, Mexico City 04510, Mexico
Guevara-Vela, Jose Manuel:
Univ Autonoma Madrid, Dept Quim Fis Aplicada, Madrid 28049, Spain
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