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Oxidation states from wave function analysis

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

Financial help from projects CTQ2011-23441/BQU, UNGI08-4E-003, and SGR528 is acknowledged. E.R-C. acknowledges support from Grant No. AP2008-01231 and from CIG No. PCI09-GA-2011-294240. V.P. acknowledges support from Grant No. BES-2012-052801 and from CTQ2011-23156/BQU

© Journal of Chemical Theory and Computation, 2015, vol. 11, núm. 4, p. 1501-1508

American Chemical Society (ACS)

Author: Ramos-Cordoba, Eloy
Postils, Verònica
Salvador Sedano, Pedro
Date: 2015 April 14
Abstract: 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
Financial help from projects CTQ2011-23441/BQU, UNGI08-4E-003, and SGR528 is acknowledged. E.R-C. acknowledges support from Grant No. AP2008-01231 and from CIG No. PCI09-GA-2011-294240. V.P. acknowledges support from Grant No. BES-2012-052801 and from CTQ2011-23156/BQU
Format: application/pdf
ISSN: 1549-9618 (versió paper)
1549-9626 (versió electrònica)
Document access: http://hdl.handle.net/10256/11353
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MICINN/PN 2012-2014/CTQ2011-23156
MICINN/PN 2012-2014/CTQ2011-23441
MEC/2008/UNGI08-4E-003
AGAUR/2009-2014/2009 SGR-528
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ct501088v
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/294240
Is part of: © Journal of Chemical Theory and Computation, 2015, vol. 11, núm. 4, p. 1501-1508
Rights: Tots els drets reservats
Subject: Orbitals moleculars
Molecular orbitals
Mecànica ondulatòria
Wave mechanics
Title: Oxidation states from wave function analysis
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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