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Characterization and quantification of polyradical character

The decomposition of 〈͈Ŝ²〉 into atomic and diatomic contributions (local spin analysis) is used to detect and quantify the polyradical character of molecular systems. A model triradical system is studied in detail, and the local spin analysis is used to distinguish several patterns of local spin distributions and spin-spin interactions that can be found for different electronic states. How close a real molecular system is to an ideal system of k perfectly localized spin centers is utilized to define a measure of its k-radical character. The spin properties and triradical character of the lowest-lying electronic states of a number of all σ, all π, and σ-π organic triradicals are discussed in detail. The local spin contributions exhibit good correlation with experimental triradical stabilization energies

Financial help has been furnished by the Spanish MICINN Projects No. CTQ2011-23441/BQU. Financial support from MICINN and the FEDER fund (European Fund for Regional Development) was also provided by grant UNG108-4E-003. Financial support from the Generalitat de Catalunya (SGR528 and Xarxa de Referencia en Quimica Teorica i Computacional) is also acknowledged. E.R-C. acknowledges support from the Spanish FPU program (Grant No. AP2008-01231) and from the EU under a Marie Curie Career Integration grant (PCI09-GA-2011-294240)

© Journal of Chemical Theory and Computation, 2014, vol. 10, p. 634-641

American Chemical Society (ACS)

Autor: Ramos-Cordoba, Eloy
Salvador Sedano, Pedro
Data: 2014
Resum: The decomposition of 〈͈Ŝ²〉 into atomic and diatomic contributions (local spin analysis) is used to detect and quantify the polyradical character of molecular systems. A model triradical system is studied in detail, and the local spin analysis is used to distinguish several patterns of local spin distributions and spin-spin interactions that can be found for different electronic states. How close a real molecular system is to an ideal system of k perfectly localized spin centers is utilized to define a measure of its k-radical character. The spin properties and triradical character of the lowest-lying electronic states of a number of all σ, all π, and σ-π organic triradicals are discussed in detail. The local spin contributions exhibit good correlation with experimental triradical stabilization energies
Financial help has been furnished by the Spanish MICINN Projects No. CTQ2011-23441/BQU. Financial support from MICINN and the FEDER fund (European Fund for Regional Development) was also provided by grant UNG108-4E-003. Financial support from the Generalitat de Catalunya (SGR528 and Xarxa de Referencia en Quimica Teorica i Computacional) is also acknowledged. E.R-C. acknowledges support from the Spanish FPU program (Grant No. AP2008-01231) and from the EU under a Marie Curie Career Integration grant (PCI09-GA-2011-294240)
Format: application/pdf
ISSN: 1549-9618 (versió paper)
1549-9626 (versió electrònica)
Accés al document: http://hdl.handle.net/10256/10335
Llenguatge: eng
Editor: American Chemical Society (ACS)
Col·lecció: MICINN/PN 2012-2014/CTQ2011-23441
AGAUR/2009-2014/2009 SGR-528
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ct401009p
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/294240
És part de: © Journal of Chemical Theory and Computation, 2014, vol. 10, p. 634-641
Drets: Tots els drets reservats
Matèria: Química quàntica
Quantum chemistry
Spin (Física nuclear)
Nuclear spin
Polarització (Física nuclear)
Polarization (Nuclear physics)
Títol: Characterization and quantification of polyradical character
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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