An Interacting Quantum Atoms Analysis of the Metal–Metal Bond in [M₂(CO)₈]ⁿ Systems

Abstract

The metal-metal interaction in policarbonyl metal clusters remains one of the most challenging and controversial issues in metal-organic chemistry, being at heart of a generalized understanding of chemical bonding and of specific applications of these molecules. In this work, the interacting quantum atoms (IQA) approach is used to study the metal-metal interaction in dimetal polycarbonyl dimers, analysing bridgedclusters. In all systems, a delocalized covalent bond is found to occur, involving the metals and the carbonyls, but the global stability of the dimers mainly originates from the coulombic attraction between the metals and the oxygens.

Halogen Bonds in Clathrate Cages: A Real Space Perspective

“…Because of this distinctive ability of separating bonding components as well as reconstructing fully the energy in a pairwise additive manner, IQA has been succesfully employed to scrutinize a variety of phenomena where there is a combination of Coulombic and quantum contributions, like the cooperativity in hydrogen bonds,, the role of covalency in metal‐metal interactions or in halogen bonding …”

“…Because of this distinctive ability of separating bonding components as well as reconstructing fully the energy in a pairwise additive manner, IQA has been succesfully employed to scrutinize a variety of phenomena where there is a combination of Coulombic and quantum contributions, like the cooperativity in hydrogen bonds, [31,32] the role of covalency in metal-metal interactions [33] or in halogen bonding. [34][35][36] Since lone pairs are an essential part of the accepted s-hole paradigm that is usually employed to describe halogen bonds, we have also used real space techniques which stress the role of these objects.…”

Where Does Electron Correlation Lie? Some Answers from a Real Space Partition

“…[12,13] Thec ombination of these methods of wavefunction analysish as been used to shed light on ab road range of problems. For example, the nature of covalent, [14,15] metallic, [16][17][18] as well as noncovalent interactions, [19][20][21][22][23][24][25][26][27][28] the origin of steric effects, [29][30][31] and the study of excited states [32][33][34] to name af ew.I QA/QTAIM provides explicit access to both one-and two-center correlation energy terms that add to the total correlatione nergy as measured with respect to deviations from the HF energy components.…”

Energetic Analysis of Conjugated Hydrocarbons Using the Interacting Quantum Atoms Method

“…In addition to the usual virial partitioning of the molecular energy defined in the QTAIM, the interacting quantum atoms method (IQA) provides an energy decomposition scheme in atomic and interaction contributions that can be applied for nonequilibrium molecular geometries . The IQA approach combined with the partitioning of real space defined in the QTAIM, has proved to be useful in the study of diverse chemical processes in the ground and excited states from an energetic point of view . In particular, using this methodology, Badri and Foroutan‐Nejad emphasized the theoretical link between the bond length, the electron sharing and the exchange interaction energy between the atoms in some aromatic molecules .…”