scholarly journals First-principles prediction of redox potentials in transition-metal compounds withLDA+U

2004 ◽  
Vol 70 (23) ◽  
Author(s):  
F. Zhou ◽  
M. Cococcioni ◽  
C. A. Marianetti ◽  
D. Morgan ◽  
G. Ceder
Keyword(s):  
Transition Metal ◽  
First Principles ◽  
Transition Metal Compounds ◽  
Redox Potentials ◽  
Metal Compounds

scholarly journals Can We Safely Obtain Formal Oxidation States from Centroids of Localized Orbitals?

Molecules ◽  
2020 ◽  
Vol 25 (1) ◽  
pp. 234 ◽  
Author(s):  
Martí Gimferrer ◽  
Gerard Comas-Vilà ◽  
Pedro Salvador
Keyword(s):  
Transition Metal ◽  
First Principles ◽  
Transition Metal Compounds ◽  
Oxidation States ◽  
Localized Orbitals ◽  
Metal Compounds ◽  
Mixed Approach ◽  
High Valent ◽  
New Criterion

The use of centroids of localized orbitals as a method to derive oxidation states (OS) from first-principles is critically analyzed. We explore the performance of the closest-atom distance criterion to assign electrons for a number of challenging systems, including high-valent transition metal compounds, π-adducts, and transition metal (TM) carbenes. Here, we also introduce a mixed approach that combines the position of the centroids with Bader’s atomic basins as an alternative criterion for electron assignment. The closest-atom criterion performs reasonably well for the challenging systems, but wrongly considers O-H and N-H bonds as hydrides. The new criterion fixes this problem, but underperforms in the case of TM carbenes. Moreover, the OS assignment in dubious cases exhibit undesirable dependence on the particular choice for orbital localization.

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