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Toward a Unique Definition of the Local Spin

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

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)

© Journal of Chemical Theory and Computation, 2012, vol. 8, núm. 4, p. 1270-1279

Author: Ramos-Cordoba, Eloy
Matito i Gras, Eduard
Mayer, István
Salvador Sedano, Pedro
Date: 2012
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
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)
Format: application/pdf
ISSN: 1549-9626
Document access: http://hdl.handle.net/10256/7127
Language: eng
Collection: MICINN/PN 2012-2014/CTQ2011-23441
MICINN/PN 2012-2014/CTQ2011-23156
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ct300050c
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/294240
Is part of: © Journal of Chemical Theory and Computation, 2012, vol. 8, núm. 4, p. 1270-1279
Rights: Tots els drets reservats
Subject: Química quàntica
Quantum chemistry
Title: Toward a Unique Definition of the Local Spin
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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