dc.creator | Jiménez Calzado, Carmen | es |
dc.creator | Cabrero, Jesús | es |
dc.creator | Malrieu, J.P. | es |
dc.creator | Caballol, Rosa | es |
dc.date.accessioned | 2016-10-28T10:32:55Z | |
dc.date.available | 2016-10-28T10:32:55Z | |
dc.date.issued | 2002 | |
dc.identifier.citation | Jiménez Calzado, C., Cabrero, J., Malrieu, J.P. y Caballol, . (2002). Analysis of the magnetic coupling in binuclear complexes. II. Derivation of valence effective Hamiltonians from ab initio Cl and DFT calculations. Journal of Chemical Physics, 116 (10), 3985-4000. | |
dc.identifier.issn | 0021-9606 | es |
dc.identifier.uri | http://hdl.handle.net/11441/48336 | |
dc.description.abstract | Most interpretations of the magnetic coupling J between two unpaired electrons rest upon simple
valence models that involve essentially the ferromagnetic direct exchange contribution, Kab , and
the antiferromagnetic effect of the delocalization resulting from the interaction between neutral and
ionic determinants, tab , whose energy difference is U. Ab initio valence-only calculations give very
poor estimates of J, whatever the definition of the magnetic orbitals, and large CI expansions are
required to evaluate it properly. It is, however, possible to define valence effective Hamiltonians
from the knowledge of the eigenenergies and the eigenvectors of these accurate CI calculations.
When applied to four different complexes, this strategy shows that spin polarization may change the
sign of the direct exchange interaction, Kab , and that dynamical correlation results in a dramatic
reduction of the effective repulsion U. The present article also shows how Kab , tab , and U effective
parameters can be extracted from density functional theory ~DFT! calculations and that the typical
overestimation of J in DFT can be attributed to an excessive lowering of the effective on-site
repulsion | es |
dc.format | application/pdf | es |
dc.language.iso | eng | es |
dc.publisher | American Institute of Physics Publising LLC | es |
dc.relation.ispartof | Journal of Chemical Physics, 116 (10), 3985-4000. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.title | Analysis of the magnetic coupling in binuclear complexes. II. Derivation of valence effective Hamiltonians from ab initio Cl and DFT calculations | es |
dc.type | info:eu-repo/semantics/article | es |
dcterms.identifier | https://ror.org/03yxnpp24 | |
dc.type.version | info:eu-repo/semantics/publishedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.contributor.affiliation | Universidad de Sevilla. Departamento de Química Física | es |
dc.relation.publisherversion | https://dx.doi.org/10.1063/1.1446024 | es |
dc.identifier.doi | 10.1063/1.1446024 | es |
idus.format.extent | 16 p. | es |
dc.journaltitle | Journal of Chemical Physics | es |
dc.publication.volumen | 116 | es |
dc.publication.issue | 10 | es |
dc.publication.initialPage | 3985 | es |
dc.publication.endPage | 4000 | es |
dc.identifier.idus | https://idus.us.es/xmlui/handle/11441/48336 | |