Oxidation
States from Wave Function Analysis
Ramos-CordobaEloy
PostilsVerò€nica
SalvadorPedro
2015
We
introduce a simple and general scheme to derive from wavefuntion
analysis the most appropriate atomic/fragment electron configurations
in a molecular system, from which oxidation states can be inferred.
The method can be applied for any level of theory for which the first-order
density matrix is available, and unlike others, it is not restricted
to transition metal complexes. The method relies on the so-called
spin-resolved effective atomic orbitals which for the present purpose
is extended here to deal with molecular fragments/ligands. We describe
in detail the most important points of the new scheme, in particular
the hierarchical fragment approach devised for practical applications.
A number of transition metal complexes with different formal oxidation
states and spin states and a set of organic and inorganic compounds
are provided as illustrative examples of the new scheme. Challenging
systems such as transition state structures are also tackled on equal
footing.