Atoms in molecules

This article provides insufficient context for those unfamiliar with the subject. Please help improve the article by providing more context for the reader. (July 2017) (Learn how and when to remove this message)

In quantum chemistry, the quantum theory of atoms in molecules (QTAIM), sometimes referred to as atoms in molecules (AIM), is a model of molecular and condensed matter electronic systems (such as crystals) in which the principal objects of molecular structure - atoms and bonds - are natural expressions of a system's observable electron density distribution function. An electron density distribution of a molecule is a probability distribution that describes the average manner in which the electronic charge is distributed throughout real space in the attractive field exerted by the nuclei. According to QTAIM, molecular structure is revealed by the stationary points of the electron density together with the gradient paths of the electron density that originate and terminate at these points.

QTAIM was primarily developed by Professor Richard Bader and his research group at McMaster University over the course of decades, beginning with analyses of theoretically calculated electron densities of simple molecules in the early 1960s and culminating with analyses of both theoretically and experimentally measured electron densities of crystals in the 90s. The development of QTAIM was driven by the assumption that, since the concepts of atoms and bonds have been and continue to be so ubiquitously useful in interpreting, classifying, predicting and communicating chemistry, they should have a well-defined physical basis.

QTAIM recovers the central operational concepts of the molecular structure hypothesis, that of a functional grouping of atoms with an additive and characteristic set of properties, together with a definition of the bonds that link the atoms and impart the structure. QTAIM defines chemical bonding and structure of a chemical system based on the topology of the electron density. In addition to bonding, QTAIM allows the calculation of certain physical properties on a per-atom basis, by dividing space up into atomic volumes containing exactly one nucleus, which acts as a local attractor of the electron density. In QTAIM an atom is defined as a proper open system, i.e. a system that can share energy and electron density which is localized in the 3D space. The mathematical study of these features is usually referred to in the literature as charge density topology.

QTAIM rests on the fact that the dominant topological property of the vast majority of electron density distributions is the presence of strong maxima that occur exclusively at the nuclei, certain pairs of which are linked together by ridges of electron density. In terms of an electron density distribution's gradient vector field, this corresponds to a complete, non-overlapping partitioning of a molecule into three-dimensional basins (atoms) that are linked together by shared two-dimensional separatrices (interatomic surfaces). Within each interatomic surface, the electron density is a maximum at the corresponding internuclear saddle point, which also lies at the minimum of the ridge between corresponding pair of nuclei, the ridge being defined by the pair of gradient trajectories (bond path) originating at the saddle point and terminating at the nuclei. Because QTAIM atoms are always bounded by surfaces having zero flux in the gradient vector field of the electron density, they have some unique quantum mechanical properties compared to other subsystem definitions, including unique electronic kinetic energy the satisfaction of an electronic virial theorem analogous to the molecular electronic virial theorem and some interesting variational properties. QTAIM has gradually become a method for addressing possible questions regarding chemical systems, in a variety of situations hardly handled before by any other model or theory in chemistry.^[1][2][3][4]