{ "dc.contributor.author": "Ramos Cordoba, Eloy" , "dc.contributor.author": "Matito i Gras, Eduard" , "dc.contributor.author": "Mayer, István" , "dc.contributor.author": "Salvador Sedano, Pedro" , "dc.date.accessioned": "2012-10-10T09:56:38Z" , "dc.date.available": "2012-10-10T09:56:38Z" , "dc.date.issued": "2012" , "dc.identifier.issn": "1549-9626" , "dc.identifier.uri": "http://hdl.handle.net/10256/7127" , "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)" , "dc.format.mimetype": "application/pdf" , "dc.language.iso": "eng" , "dc.relation": "MICINN/PN 2012-2014/CTQ2011-23441" , "dc.relation": "MICINN/PN 2012-2014/CTQ2011-23156" , "dc.relation.isformatof": "Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ct300050c" , "dc.relation.ispartof": "© Journal of Chemical Theory and Computation, 2012, vol. 8, núm. 4, p. 1270-1279" , "dc.relation.ispartofseries": "Articles publicats (D-Q)" , "dc.rights": "Tots els drets reservats" , "dc.subject": "Química quàntica" , "dc.subject": "Quantum chemistry" , "dc.title": "Toward a Unique Definition of the Local Spin" , "dc.type": "info:eu-repo/semantics/article" , "dc.rights.accessRights": "info:eu-repo/semantics/embargoedAccess" , "dc.relation.projectID": "info:eu-repo/grantAgreement/EC/FP7/294240" , "dc.type.version": "info:eu-repo/semantics/publishedVersion" , "dc.identifier.doi": "http://dx.doi.org/10.1021/ct300050c" , "dc.identifier.idgrec": "016130" , "dc.contributor.funder": "Ministerio de Ciencia e Innovación (Espanya)" }