Breakdown of the mirror image symmetry in the optical absorption/emission spectra of oligo(para-phenylene)s

Georg Heimel; Maria Daghofer; Johannes Gierschner; Emil J.W. List; Andrew C. Grimsdale; Klaus Müllen; David Beljonne; Jean Luc Brédas; Egbert Zojer

doi:10.1063/1.1839574

Breakdown of the mirror image symmetry in the optical absorption/emission spectra of oligo(para-phenylene)s

Georg Heimel, Maria Daghofer, Johannes Gierschner, Emil J.W. List, Andrew C. Grimsdale, Klaus Müllen, David Beljonne, Jean Luc Brédas, Egbert Zojer

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124 Scopus citations

Abstract

The absorption and emission spectra of most luminescent, π-conjugated, organic molecules are the mirror image of each other. In some cases, however, this symmetry is severely broken. In the present work, the asymmetry between the absorption and fluorescence spectra in molecular systems consisting of para-linked phenyl rings is studied. The vibronic structure of the emission and absorption bands is calculated from ab initio quantum chemical methods and a subsequent, rigorous Franck-Condon treatment. Good agreement with experiment is achieved. A clear relation can be established between the strongly anharmonic double-well potential for the phenylene ring librations around the long molecular axis and the observed deviation from the mirror image symmetry. Consequences for related compounds and temperature dependent optical measurements are also discussed.

Original language	English (US)
Article number	054501
Journal	JOURNAL OF CHEMICAL PHYSICS
Volume	122
Issue number	5
DOIs	https://doi.org/10.1063/1.1839574
State	Published - 2005
Externally published	Yes

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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title = "Breakdown of the mirror image symmetry in the optical absorption/emission spectra of oligo(para-phenylene)s",

abstract = "The absorption and emission spectra of most luminescent, π-conjugated, organic molecules are the mirror image of each other. In some cases, however, this symmetry is severely broken. In the present work, the asymmetry between the absorption and fluorescence spectra in molecular systems consisting of para-linked phenyl rings is studied. The vibronic structure of the emission and absorption bands is calculated from ab initio quantum chemical methods and a subsequent, rigorous Franck-Condon treatment. Good agreement with experiment is achieved. A clear relation can be established between the strongly anharmonic double-well potential for the phenylene ring librations around the long molecular axis and the observed deviation from the mirror image symmetry. Consequences for related compounds and temperature dependent optical measurements are also discussed.",

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language = "English (US)",

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T1 - Breakdown of the mirror image symmetry in the optical absorption/emission spectra of oligo(para-phenylene)s

AU - Heimel, Georg

AU - Daghofer, Maria

AU - Gierschner, Johannes

AU - List, Emil J.W.

AU - Grimsdale, Andrew C.

AU - Müllen, Klaus

AU - Beljonne, David

AU - Brédas, Jean Luc

AU - Zojer, Egbert

PY - 2005

Y1 - 2005

N2 - The absorption and emission spectra of most luminescent, π-conjugated, organic molecules are the mirror image of each other. In some cases, however, this symmetry is severely broken. In the present work, the asymmetry between the absorption and fluorescence spectra in molecular systems consisting of para-linked phenyl rings is studied. The vibronic structure of the emission and absorption bands is calculated from ab initio quantum chemical methods and a subsequent, rigorous Franck-Condon treatment. Good agreement with experiment is achieved. A clear relation can be established between the strongly anharmonic double-well potential for the phenylene ring librations around the long molecular axis and the observed deviation from the mirror image symmetry. Consequences for related compounds and temperature dependent optical measurements are also discussed.

AB - The absorption and emission spectra of most luminescent, π-conjugated, organic molecules are the mirror image of each other. In some cases, however, this symmetry is severely broken. In the present work, the asymmetry between the absorption and fluorescence spectra in molecular systems consisting of para-linked phenyl rings is studied. The vibronic structure of the emission and absorption bands is calculated from ab initio quantum chemical methods and a subsequent, rigorous Franck-Condon treatment. Good agreement with experiment is achieved. A clear relation can be established between the strongly anharmonic double-well potential for the phenylene ring librations around the long molecular axis and the observed deviation from the mirror image symmetry. Consequences for related compounds and temperature dependent optical measurements are also discussed.

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M3 - Article

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Breakdown of the mirror image symmetry in the optical absorption/emission spectra of oligo(para-phenylene)s

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