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arXiv · 1111.0894

Hilbert-space partitioning of the molecular one-electron density matrix with orthogonal projectors

Diederik Vanfleteren·Dimitri Van Neck·Patrick Bultinck·Paul W. Ayers·Michel Waroquier
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Abstract

A double-atom partitioning of the molecular one-electron density matrix is used to describe atoms and bonds. All calculations are performed in Hilbert space. The concept of atomic weight functions (familiar from Hirshfeld analysis of the electron density) is extended to atomic weight matrices. These are constructed to be orthogonal projection operators on atomic subspaces, which has significant advantages in the interpretation of the bond contributions. In close analogy to the iterative Hirshfeld procedure, self-consistency is built in at the level of atomic charges and occupancies. The method is applied to a test set of about 67 molecules, representing various types of chemical binding. A close correlation is observed between the atomic charges and the Hirshfeld-I atomic charges.

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Diederik Vanfleteren, Dimitri Van Neck, Patrick Bultinck, Paul W. Ayers, Michel Waroquier. 2011-11-03. Hilbert-space partitioning of the molecular one-electron density matrix with orthogonal projectors. https://doi.org/10.1063/1.3521493

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