Toward a Unique Definition of the Local Spin
dc.contributor.author
dc.date.accessioned
2012-10-10T09:56:38Z
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2012-10-10T09:56:38Z
dc.date.issued
2012
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dc.description.abstract
In this work, we demonstrate that there is a continuum of different formulations for the decomposition of Ŝ2 that fulfills all physical requirements imposed to date. We introduce a new criterion based upon the behavior of single-electron systems to fix the value of the parameter defining that continuum, and thus we put forward a new general formula applicable for both single-determinant and correlated wave functions. The numerical implementation has been carried out in the three-dimensional physical space for several atomic definitions. A series of representative closed-shell and open-shell systems have been used to illustrate the performance of this new decomposition scheme against other existing approaches. Unlike other decompositions of Ŝ2, the new scheme provides very small local-spin values for genuine diamagnetic molecules treated with correlated wave functions, in conformity with the physical expectations
dc.description.sponsorship
Financial help has been furnished by the Spanish MICINN Project Nos. CTQ2011-23441/BQU and CTQ2011-23156/BQU and Accion Complementaria del MCI (PCI2006-A7-0631). Financial support from MICINN and the FEDER fund (European Fund for Regional Development) was also provided by grant UNGI08-4E-003. E.R.-C. acknowledges support from the Spanish FPU program (Grant No. AP2008-01231). E.M. acknowledges financial support from the EU under a Marie Curie Career Integration grant (PCI09-GA-2011-294240) and the Beatriu de Pinos program from AGAUR for the postdoctoral grant (BP_B_00236). I.M. acknowledges partial financial support from the Hungarian Scientific Research Fund (grant OTKA 71816)
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application/pdf
dc.language.iso
eng
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2011-23441/ES/NUEVOS ENFOQUES PARA EL ESTUDIO COMPUTACIONAL DE BIOMOLECULAS, INTERACCIONES DE ESPIN EN AGREGADOS METALICOS Y SISTEMAS MOLECULARES DE ALMACENAMIENTO DE HIDROGENO/
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/
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Versió postprint del document publicat a: http://dx.doi.org/10.1021/ct300050c
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© Journal of Chemical Theory and Computation, 2012, vol. 8, núm. 4, p. 1270-1279
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Toward a Unique Definition of the Local Spin
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/294240/EU/Development of new non-empirical DFT functionals./NEWDFTFUNCT
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
016130
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dc.relation.FundingProgramme
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dc.identifier.eissn
1549-9626