Energy decomposition analysis of metal-metal bonding in [M2X8](2-) (X = Cl, Br) complexes of 5f (U, Np, Pu), 5d (W, Re, Os), and 4d (Mo, Tc, Ru) elements
-
Altmetric Citations
Cavigliasso, German; Kaltsoyannis, Nikolas
Description
The electronic structures of a series of [M2X8] 2- (X = Cl, Br) complexes involving 5f (U, Np, Pu), 5d (W, Re, Os), and 4d (Mo, Tc, Ru) elements have been calculated using density functional theory, and an energy decomposition approach has been used to carry out a detailed analysis of the metal-metal interactions. The energy decomposition analysis involves contributions from orbital interactions (mixing of occupied and unoccupied orbitals), electrostatic effects (Coulombic attraction and...[Show more]
dc.contributor.author | Cavigliasso, German | |
---|---|---|
dc.contributor.author | Kaltsoyannis, Nikolas | |
dc.date.accessioned | 2015-12-10T21:56:11Z | |
dc.identifier.issn | 0020-1669 | |
dc.identifier.uri | http://hdl.handle.net/1885/39310 | |
dc.description.abstract | The electronic structures of a series of [M2X8] 2- (X = Cl, Br) complexes involving 5f (U, Np, Pu), 5d (W, Re, Os), and 4d (Mo, Tc, Ru) elements have been calculated using density functional theory, and an energy decomposition approach has been used to carry out a detailed analysis of the metal-metal interactions. The energy decomposition analysis involves contributions from orbital interactions (mixing of occupied and unoccupied orbitals), electrostatic effects (Coulombic attraction and repulsion), and Pauli repulsion (associated with four-electron two-orbital interactions). As previously observed for Mo, W, and U M2X 6 species, the general results suggest that the overall metal-metal interaction is considerably weaker or unfavorable in the actinide systems relative to the d-block analogues, as a consequence of a significantly more destabilizing contribution from the combined Pauli and electrostatic (prerelaxation) effects. Although the orbital-mixing (postrelaxation) contribution to the total bonding energy is predicted to be larger in the actinide complexes, this is not sufficiently strong to compensate for the comparatively greater destabilization originating from the Pauli-plus- electrostatic effects. A generally weak electrostatic contribution accounts for the large prerelaxation destabilization in the f-block systems, and ultimately for the weak or unfavorable nature of metal-metal bonding between the actinide elements. There is a greater variation in the energy decomposition results across the [M2Cl8]2- series for the actinide than for the d-block elements, both in the general behavior and in some particular properties. | |
dc.publisher | American Chemical Society | |
dc.source | Inorganic Chemistry | |
dc.title | Energy decomposition analysis of metal-metal bonding in [M2X8](2-) (X = Cl, Br) complexes of 5f (U, Np, Pu), 5d (W, Re, Os), and 4d (Mo, Tc, Ru) elements | |
dc.type | Journal article | |
local.description.notes | Imported from ARIES | |
local.identifier.citationvolume | 46 | |
dc.date.issued | 2007 | |
local.identifier.absfor | 030102 - Electroanalytical Chemistry | |
local.identifier.ariespublication | u3379551xPUB175 | |
local.type.status | Published Version | |
local.contributor.affiliation | Cavigliasso, German, College of Physical and Mathematical Sciences, ANU | |
local.contributor.affiliation | Kaltsoyannis, Nikolas, University College London | |
local.description.embargo | 2037-12-31 | |
local.bibliographicCitation.issue | 9 | |
local.bibliographicCitation.startpage | 3557 | |
local.bibliographicCitation.lastpage | 3565 | |
local.identifier.doi | 10.1021/ic0623260 | |
local.identifier.absseo | 970103 - Expanding Knowledge in the Chemical Sciences | |
dc.date.updated | 2015-12-09T07:35:16Z | |
local.identifier.scopusID | 2-s2.0-34248357864 | |
Collections | ANU Research Publications |
Download
File | Description | Size | Format | Image |
---|---|---|---|---|
01_Cavigliasso_Energy_decomposition_analysis_2007.pdf | 189.68 kB | Adobe PDF | Request a copy |
Items in Open Research are protected by copyright, with all rights reserved, unless otherwise indicated.
Updated: 17 November 2022/ Responsible Officer: University Librarian/ Page Contact: Library Systems & Web Coordinator