The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center

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 vib...

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Authors: Torrent Sucarrat, Miquel, Luis Luis, Josep Maria, Solà i Puig, Miquel
Format: article
Status:Versión aceptada para publicación
Publication Date:2005
Country:España
Institution:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repository:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/16570
Online Access:http://hdl.handle.net/10256/16570
Access Level:Open access
Keyword:Polarització (Electricitat)
Polarization (Electricity)
Dinàmica molecular
Molecular dynamics
Funcional de densitat, Teoria del
Density functionals
Aromaticitat (Química)
Aromaticity (Chemistry)
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spelling The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic CenterTorrent Sucarrat, MiquelLuis Luis, Josep MariaSolà i Puig, MiquelPolarització (Electricitat)Polarization (Electricity)Dinàmica molecularMolecular dynamicsFuncional de densitat, Teoria delDensity functionalsAromaticitat (Química)Aromaticity (Chemistry)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 aromaticitySupport 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, 2001WileyMinisterio de Ciencia y Tecnología (Espanya)2005info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionpeer-reviewed8 p.application/pdfhttp://hdl.handle.net/10256/16570http://hdl.handle.net/10256/16570© Chemistry-A European Journal, 2005, vol. 11, núm. 20, p. 6024-6031Articles publicats (D-Q)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 6031reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1002/chem.200500223info:eu-repo/semantics/altIdentifier/issn/0947-6539info:eu-repo/semantics/altIdentifier/eissn/1521-3765MICYT/PN 2002-2005/BQU2002-04112-C02-02MICYT/PN 2002-2005/BQU2002-03334Tots els drets reservatsinfo:eu-repo/semantics/openAccessoai:recercat.cat:10256/165702026-05-29T05:05:01Z
dc.title.none.fl_str_mv The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center
title The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center
spellingShingle The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center
Torrent Sucarrat, Miquel
Polarització (Electricitat)
Polarization (Electricity)
Dinàmica molecular
Molecular dynamics
Funcional de densitat, Teoria del
Density functionals
Aromaticitat (Química)
Aromaticity (Chemistry)
title_short The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center
title_full The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center
title_fullStr The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center
title_full_unstemmed The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center
title_sort The Breakdown of the Minimum Polarizability Principle in Vibrational Motions as an Indicator of the Most Aromatic Center
dc.creator.none.fl_str_mv Torrent Sucarrat, Miquel
Luis Luis, Josep Maria
Solà i Puig, Miquel
author Torrent Sucarrat, Miquel
author_facet Torrent Sucarrat, Miquel
Luis Luis, Josep Maria
Solà i Puig, Miquel
author_role author
author2 Luis Luis, Josep Maria
Solà i Puig, Miquel
author2_role author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia y Tecnología (Espanya)
dc.subject.none.fl_str_mv Polarització (Electricitat)
Polarization (Electricity)
Dinàmica molecular
Molecular dynamics
Funcional de densitat, Teoria del
Density functionals
Aromaticitat (Química)
Aromaticity (Chemistry)
topic Polarització (Electricitat)
Polarization (Electricity)
Dinàmica molecular
Molecular dynamics
Funcional de densitat, Teoria del
Density functionals
Aromaticitat (Química)
Aromaticity (Chemistry)
description 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
publishDate 2005
dc.date.none.fl_str_mv 2005
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
peer-reviewed
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/16570
http://hdl.handle.net/10256/16570
url http://hdl.handle.net/10256/16570
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.200500223
info:eu-repo/semantics/altIdentifier/issn/0947-6539
info:eu-repo/semantics/altIdentifier/eissn/1521-3765
MICYT/PN 2002-2005/BQU2002-04112-C02-02
MICYT/PN 2002-2005/BQU2002-03334
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 8 p.
application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv © Chemistry-A European Journal, 2005, vol. 11, núm. 20, p. 6024-6031
Articles publicats (D-Q)
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
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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