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Remarks on the concept of an atom in a molecule and on charge transfer between atoms on molecule formation

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TLDR
In this paper, the density functional theory is used to define an atom in a molecule in its ground state: the molecular electron density is the sum of atomic densities, the atoms have the same chemical potential as does the molecule, and the atoms are minimally promoted from their ground states.
Abstract
Density functional theory provides a natural and rigorous definition of an atom in a molecule in its ground state: The molecular electron density is the sum of atomic densities, the atoms have the same chemical potential as does the molecule, and the atoms are minimally promoted from their ground states. These atoms in general are not spherical, and in general they bear nonintegral charges. Charge transfer on molecule formation is thereby uniquely defined. Calculations by Palke and by Guse are reviewed, in which the hydrogen atom is identified in the hydrogen molecule.

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Citations
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Journal ArticleDOI

Information theory, atoms in molecules, and molecular similarity

TL;DR: Using information theory, it is argued that from among possible definitions of what an atom is when it is in a molecule, a particular one merits special attention and is the atom defined by the "stockholders partitioning" of a molecule invented by Hirshfeld.
Journal ArticleDOI

Atoms in molecules, an axiomatic approach. I. Maximum transferability

TL;DR: In this article, an axiomatic basis for the concept of an atom within a molecule, with particular emphasis devoted to the definition of transferability and the atomic description of Hirshfeld, is presented.
Journal ArticleDOI

Electron flow and electronegativity equalization in the process of bond formation

TL;DR: In this paper, the second-order perturbation theory was used to analyze electron flow and electronegativity equalization in the process of bond formation, and it was shown that the bond hardness is related to the matrix elements of the fragment-electron count operator.
Journal ArticleDOI

Density Functional Partition Theory with Fractional Occupations.

TL;DR: This work gives the full formalism of density functional partition theory (DFPT) and illustrates DFPT in the general case of noninteger fragment occupations.
Journal ArticleDOI

Density-functional and Hydrodynamical Approach to Ion-Atom Collisions Through a New Generalized Nonlinear Schrödinger Equation

TL;DR: A single-particle time-dependent single density equation for many-electron systems is derived, a new generalized nonlinear Schroedinger equation whose solution directly yields the time- dependent charge density, current density, and a pulsating effective potential surface on which the process occurs.
References
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Journal ArticleDOI

Absolute hardness: companion parameter to absolute electronegativity

TL;DR: In this paper, a property called absolute hardness eta is defined for neutral and charged species, atomic and molecular, for both hard and soft acids and bases, by making use of the hypothesis that extra stability attends bonding of A to B when the ionization potentials of A and B in the molecule are the same.
Journal ArticleDOI

Electronegativity: The density functional viewpoint

TL;DR: The concept of electronegativity is defined in this paper as the negative of the chemical potential (the Lagrange multiplier for the normalization constraint) in the Hohenberg-Kohn density functional theory of the ground state: χ =−μ=−(∂E/∂N)v.
Journal ArticleDOI

Density-Functional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy

TL;DR: The Hohenberg-Kohn theorem was extended to fractional electron number for an isolated open system described by a statistical mixture in this article, and the curve of lowest average energy was found to be a series of straight line segments with slope discontinuities at integral $N.
Book ChapterDOI

Quantum Theory of Atoms in Molecules–Dalton Revisited

TL;DR: In this article, it is demonstrated that the topological property that defines the atom determines the definition of its average properties, and that the quantum mechanics has been shown to account for the properties of isolated atoms and for the total properties of a molecular system.
Journal ArticleDOI

Some remarks on the density functional theory of few-electron systems

TL;DR: In this paper, a reformulation de la theorie de la fonctionnelle densite en remplacant la densite electronique, l, par le produit du nombre d'electrons, W, and d'un facteur de forme σ.
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