The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center
dc.contributor.author
dc.date.accessioned
2019-05-06T07:26:34Z
dc.date.available
2019-05-06T07:26:34Z
dc.date.issued
2005-10-07
dc.identifier.issn
0947-6539
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dc.description.abstract
In previous works, we have shown that bond length alternation vibrational modes in -conjugated organic molecules may break the minimum polarizability principle (MPP). To arrive at this conclusion, we have developed a method that diagonalizes the polarizability Hessian matrix with respect to the vibrational nontotally symmetric normal coordinates. The vibrational motions that disobey the MPP in -conjugated molecules are distortions of the equilibrium geometry that produce a reduction of the polarizability due to the localization of -electrons. For aromatic species, this electronic localization is responsible for the subsequent reduction of the aromaticity of the system. In the present work, we apply our methodology to calculate the nontotally symmetric distortions that produce the maximum breakdown of the MPP in a series of twenty polycyclic aromatic hydrocarbons. It is shown that the nuclear displacements that break the MPP have larger components in those rings that possess the highest local aromaticity. Thus, these vibrational motions can be use as an indicator of local aromaticity
dc.description.sponsorship
Support for this work from the Spanish Ministerio de Ciencia y
Tecnología (projects No. BQU2002-04112-C02-02 and BQU2002-03334), from the
DURSI (Generalitat de Catalunya) (project 2001SGR-00290), and the use of the
computational facilities of the Catalonia Supercomputer Center (CESCA) are gratefully
acknowledged. M. T.-S. is financed through CIRIT Project No. FI/01-000699 from the
Generalitat de Catalunya. M. S. thanks the DURSI for financial support through the
Distinguished University Research Promotion, 2001
dc.format.extent
8 p.
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application/pdf
dc.language.iso
eng
dc.publisher
Wiley
dc.relation
MICYT/PN 2002-2005/BQU2002-04112-C02-02
MICYT/PN 2002-2005/BQU2002-03334
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Versió popstprint del document publicat a: https://doi.org/10.1002/chem.200500223
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© Chemistry-A European Journal, 2005, vol. 11, núm. 20, p. 6024-6031
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Articles publicats (D-Q)
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Tots els drets reservats
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Torrent Sucarrat, Miquel Luis Luis, Josep Maria Solà i Puig, Miquel 2005 The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center Chemistry-A European Journal 11 20 6024 6031
dc.subject
dc.title
The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center
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
003880
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.identifier.eissn
1521-3765