Ab initio Hartree-Fock Investigation of π-Conjugated Compounds Presenting Large βv/βe Ratio: Merocyanines

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Title:Ab initio Hartree-Fock Investigation of π-Conjugated Compounds Presenting Large βv/βe Ratio: Merocyanines
Creators:
Champagne, Benoît
Legrand, Thierry
Perpete, Eric A.
Quinet, Olivier
André, Jean-Marie
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 63, 9, pp. 1295-1308
Uncontrolled Keywords:<i>Ab initio</i> calculations, Merocyanines, Electronic and vibrational first hyperpolarizabilities, <i>Ab initio</i> coupled Hartree-Fock

Abstract

CHF/6-311G* calculations of the first electronic and vibrational hyperpolarizabilities reveal that merocyanines present a substantial β<sup>v</sup>/β<sup>e</sup> ratio under their quinonoid nonpolar form. It originates from a large vibrational first hyperpolarizability whereas its electronic counterpart is small for this class of push-pull π-conjugated molecules. The transition from the quinonoid to the aromatic configuration is accompanied by an increase of β<sup>e</sup> and a decrease of the β<sup>v</sup>/β<sup>e</sup> ratio as well as by a ≈ 180° rotation in the plane of the molecule of β<sup>e</sup> and β<sup>v</sup> with respect to the molecular frame. Our results support the recent experimental discovery that antiparallel aggregation of aromatic and quinonoid forms of merocyanine is energetically favoured and that their first hyperpolarizabilities, which combine constructively, present both electronic and non purely electronic origins.

Title:Ab initio Hartree-Fock Investigation of π-Conjugated Compounds Presenting Large βv/βe Ratio: Merocyanines
Creators:
Champagne, Benoît
Legrand, Thierry
Perpete, Eric A.
Quinet, Olivier
André, Jean-Marie
Uncontrolled Keywords:<i>Ab initio</i> calculations, Merocyanines, Electronic and vibrational first hyperpolarizabilities, <i>Ab initio</i> coupled Hartree-Fock
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:63
Number:9
Page Range:pp. 1295-1308
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19981295UNSPECIFIED
ID Code:1381
Item Type:Article
Deposited On:06 Feb 2009 17:09
Last Modified:06 Feb 2009 16:09

Citation

Champagne, Benoît; Legrand, Thierry; Perpete, Eric A.; Quinet, Olivier; André, Jean-Marie (1998) Ab initio Hartree-Fock Investigation of π-Conjugated Compounds Presenting Large βv/βe Ratio: Merocyanines. Collection of Czechoslovak Chemical Communications, 63 (9). pp. 1295-1308. ISSN 0010-0765

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