Evaluation of the Analogy between Exceptions to the Generalized Maximum Hardness Principle for Non-Totally Symmetric Vibrations and the Pseudo Jahn-Teller Effect
dc.contributor.author
dc.date.accessioned
2019-05-03T07:57:56Z
dc.date.available
2019-05-03T07:57:56Z
dc.date.issued
2003-08-22
dc.identifier.issn
1089-5639
dc.identifier.uri
dc.description.abstract
Exceptions to the generalized maximum hardness principle (MHP) for nitrogen heterocycles, along non-totally symmetric vibrations (bond-length alternating modes), are caused by pseudo-Jahn-Teller (PJT) coupling between the ground and the excited state along those modes. Thus, the PJT effect causes an increase of the energy gap between the ground and the excited state, and this is reflected in an increase of hardness. This relationship is based on the assumption that the hardness (defined as difference between ionization potential and electron affinity) is approximately equal to the HOMO-LUMO gap (Koopmans' approximation), and this is in turn assumed to be approximately equal to the energy difference between ground and excited state. The analogy is valid here because the excited state and the relevant vibration have the same symmetry, and the geometry and force constants of the optimized minima for the two coupled states are reasonably similar
dc.description.sponsorship
Support for this work under Grants No. BQU2002-04112-C02-02 and
BQU2002-03334 from the Dirección General de Enseñanza Superior e Investigación Científica y
Técnica (MEC-Spain) is acknowledged. L. B. is financed by the Ramón y Cajal program from the
Spanish Ministerio de Ciencia y Tecnología. M. T.-S. is financed through CIRIT Project No. FI/01-
000699 from the Generalitat de Catalunya. M. S. thanks the DURSI (Generalitat de Catalunya) for
financial support through the Distinguished University Research Promotion, 2001
dc.format.extent
3 p.
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
MICYT/PN 2002-2005/BQU2002-04112-C02-02
MICYT/PN 2002-2005/BQU2002-03334
dc.relation.isformatof
Versió postprint del document publicat a: https://doi.org/10.1021/jp034557n
dc.relation.ispartof
© Journal of Physical Chemistry A, 2003, vol. 107, núm. 38, p. 7337-7339
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.source
Blancafort San José, Lluís Torrent Sucarrat, Miquel Luis Luis, Josep Maria Duran i Portas, Miquel Solà i Puig, Miquel 2003 Evaluation of the Analogy between Exceptions to the Generalized Maximum Hardness Principle for Non-Totally Symmetric Vibrations and the Pseudo Jahn-Teller Effect Journal of Physical Chemistry A 107 38 7337 7339
dc.title
Evaluation of the Analogy between Exceptions to the Generalized Maximum Hardness Principle for Non-Totally Symmetric Vibrations and the Pseudo Jahn-Teller Effect
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
003301
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.identifier.eissn
1520-5215