Analysis of the sign reversal of the second-order molecular polarizability in polymethineimine chains

Denis Jacquemin, David Beljonne, Benoît Champagne, Victor Geskin, Jean Luc Brédas, Jean-Marie André

Research output: Contribution to journalArticle

Abstract

The computation of second-order polarizability tensor (β) components of polymethineimine oligomers was done with the semiempirical intermediate neglect of differential overlap (INDO) coupled either to finite-field real space or sum-over-states (SOS) approach. The sign reversal of the longitudinal β component was rationalized with chain length. Using a four-state SOS model, it was demonstrated that the shape of the β curve could be explained as resulting from the competition between two contributions of opposite signs. Those contributions were found to correspond to bond polarization and bond charge phenomena, in the framework of a real-space approach.

Original languageEnglish
Pages (from-to)6766-6774
Number of pages9
JournalThe journal of chemical physics
Volume115
Issue number14
DOIs
Publication statusPublished - 8 Oct 2001

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Chain length
Oligomers
Tensors
Polarization
oligomers
tensors
curves
polarization

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abstract = "The computation of second-order polarizability tensor (β) components of polymethineimine oligomers was done with the semiempirical intermediate neglect of differential overlap (INDO) coupled either to finite-field real space or sum-over-states (SOS) approach. The sign reversal of the longitudinal β component was rationalized with chain length. Using a four-state SOS model, it was demonstrated that the shape of the β curve could be explained as resulting from the competition between two contributions of opposite signs. Those contributions were found to correspond to bond polarization and bond charge phenomena, in the framework of a real-space approach.",
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Analysis of the sign reversal of the second-order molecular polarizability in polymethineimine chains. / Jacquemin, Denis; Beljonne, David; Champagne, Benoît; Geskin, Victor; Brédas, Jean Luc; André, Jean-Marie.

In: The journal of chemical physics, Vol. 115, No. 14, 08.10.2001, p. 6766-6774.

Research output: Contribution to journalArticle

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AU - Beljonne, David

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AU - André, Jean-Marie

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