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WIREs Comput Mol Sci
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Energy decomposition analysis

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Abstract The energy decomposition analysis (EDA) is a powerful method for a quantitative interpretation of chemical bonds in terms of three major expressions. The instantaneous interaction energy ΔEint between two fragments A and B in a molecule A–B is partitioned in three terms, namely, (1) the quasiclassical electrostatic interaction ΔEelstat between the fragments, (2) the repulsive exchange (Pauli) interaction ΔEPauli between electrons of the two fragments having the same spin, and (3) the orbital (covalent) interaction ΔEorb, which comes from the orbital relaxation and the orbital mixing between the fragments. The latter term can be decomposed into contributions of orbitals with different symmetry, which makes it possible to distinguish between σ, π, and δ bonding. After a short introduction into the theoretical background of the EDA, we present illustrative examples of main group and transition metal chemistry. The results show that the EDA terms can be interpreted in a chemically meaningful way, thus providing a bridge between quantum chemical calculations and heuristic bonding models of traditional chemistry. © 2011 John Wiley & Sons, Ltd. This article is categorized under: Structure and Mechanism > Molecular Structures

Fragments, which are used for the EDA (a) of benzene and (b) 1,3,5,7‐octatetraene. OS, open shell singlet; D, doublet.

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Schematic representation of the six sd5 hybrid orbitals. Taken from Ref 63.

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MO correlation diagram between Mo and (ZnH)12 in [Mo(ZnH)12]. Each fragment is in its septet state. (Reprinted with permission from Ref 11. Copyright 2009 John Wiley & Sons.)

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X‐ray structure of [Mo(ZnCp*)3(ZnMe)12]. Mo, red; Zn, green; C, grey. (Reprinted with permission from Ref 63. Copyright 2008 John Wiley & Sons.)

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MO correlation diagram between a d6 transition metal with the electronic configuration (a1g)2(e2g)4(e1g)0 and a cyclic 12π aromatic sandwich ligand. Shapes of the orbitals have been taken from the Bz2 ligand. The orbitals of (Cp2)2− look very similar. (Reprinted with permission from Ref 56. Copyright 2003 American Chemical Society.)

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Top, Schematic representation of the tautomers ‘normal’ N‐heterocyclic carbene (nNHC), ‘abnormal’ N‐heterocyclic carbene (aNHC), and imidazol (IMID). Bottom, Schematic representation of the complexes of the above ligands with W(CO)5.

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Schematic representations of interactions according to the Dewar–Chatt–Duncanson model. (a) and (b), σ‐donation and π‐back donation in an interaction between a transition metal (TM) and a carbonyl (CO); (c) and (d), σ‐donation and π‐back donation in an interaction between a TM and a CC double or triple bond; (e) and (f), additional possible contributions of π‐donation and δ‐back donation in the interaction between a TM and a CCtriple bond; (g) and (h), σ‐donation and π‐back donation in singlet carbene complexes.

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Top, Equilibrium geometries of benzene and cyclobutadiene and distorted geometries, which were used in the EDA calculations in Ref 23. Bottom, Schematic representation of the two fragments (colored in red and blue), which were used for the EDA calculations in Ref 23.

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