Molecular fluorescence lifetime fluctuations: On the possible role of conformational effects

Renaud A.L. Vallée; G. J. Vancso; N. F. van Hulst; J. P. Calbert; J. Cornil; J. L. Brédas

doi:10.1016/S0009-2614(03)00379-8

Molecular fluorescence lifetime fluctuations: On the possible role of conformational effects

Renaud A.L. Vallée^*, G. J. Vancso, N. F. van Hulst, J. P. Calbert, J. Cornil, J. L. Brédas

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

16 Scopus citations

Abstract

The radiative lifetime of single 1,1^′-dioctadecyl-3,3,3′, 3′-tetramethylindodicarbocyanine molecules, embedded in a polymer thin film, has been characterized. At room temperature the chemically identical molecules exhibit strong fluctuations in their fluorescence lifetime. The possible conformational origin of these fluctuations has been addressed by semi-empirical quantum-chemical calculations. Specifically, the impact of conformational effects induced by thermal motion on the transition energy and the value of the transition dipole moment has been studied. The results indicate that the strong fluctuations cannot be explained by pure thermally activated conformational changes. Since quenching mechanisms are not responsible for the observed fluctuations, we suggest that molecular segmental dynamics of the surrounding polymer play a key role in determining the lifetime fluctuations.

Original language	English (US)
Pages (from-to)	282-287
Number of pages	6
Journal	Chemical Physics Letters
Volume	372
Issue number	1-2
DOIs	https://doi.org/10.1016/S0009-2614(03)00379-8
State	Published - Apr 22 2003
Externally published	Yes

Bibliographical note

Funding Information:
R.A.L. Vallée is grateful to the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (NWO-CW) for supporting this research. The work in Arizona is supported by the National Science Foundation (CHE-0078819), the Petroleum Research Fund, and the IBM Shared University Research Program. The work in Mons is supported by the Belgian Federal Government ‘InterUniversity Attraction Pole in Supramolecular Chemistry and Catalysis (PAI 4/11)’, and the Belgian National Fund for Scientific Research (FNRS-FRFC). J.C. is an FNRS research associate; J.P.C. acknowledges a grant from the Fonds pour la Formation à la Recherche dans l’Industrie et dans l’Agriculture (FRIA).

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

Access to Document

10.1016/S0009-2614(03)00379-8

Cite this

@article{d5efb2d1fec2464f92e4a90f3594a367,

title = "Molecular fluorescence lifetime fluctuations: On the possible role of conformational effects",

abstract = "The radiative lifetime of single 1,1′-dioctadecyl-3,3,3′, 3′-tetramethylindodicarbocyanine molecules, embedded in a polymer thin film, has been characterized. At room temperature the chemically identical molecules exhibit strong fluctuations in their fluorescence lifetime. The possible conformational origin of these fluctuations has been addressed by semi-empirical quantum-chemical calculations. Specifically, the impact of conformational effects induced by thermal motion on the transition energy and the value of the transition dipole moment has been studied. The results indicate that the strong fluctuations cannot be explained by pure thermally activated conformational changes. Since quenching mechanisms are not responsible for the observed fluctuations, we suggest that molecular segmental dynamics of the surrounding polymer play a key role in determining the lifetime fluctuations.",

author = "Vall{\'e}e, {Renaud A.L.} and Vancso, {G. J.} and {van Hulst}, {N. F.} and Calbert, {J. P.} and J. Cornil and Br{\'e}das, {J. L.}",

note = "Funding Information: R.A.L. Vall{\'e}e is grateful to the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (NWO-CW) for supporting this research. The work in Arizona is supported by the National Science Foundation (CHE-0078819), the Petroleum Research Fund, and the IBM Shared University Research Program. The work in Mons is supported by the Belgian Federal Government {\textquoteleft}InterUniversity Attraction Pole in Supramolecular Chemistry and Catalysis (PAI 4/11){\textquoteright}, and the Belgian National Fund for Scientific Research (FNRS-FRFC). J.C. is an FNRS research associate; J.P.C. acknowledges a grant from the Fonds pour la Formation {\`a} la Recherche dans l{\textquoteright}Industrie et dans l{\textquoteright}Agriculture (FRIA).",

year = "2003",

month = apr,

day = "22",

doi = "10.1016/S0009-2614(03)00379-8",

language = "English (US)",

volume = "372",

pages = "282--287",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier B.V.",

number = "1-2",

}

TY - JOUR

T1 - Molecular fluorescence lifetime fluctuations

T2 - On the possible role of conformational effects

AU - Vallée, Renaud A.L.

AU - Vancso, G. J.

AU - van Hulst, N. F.

AU - Calbert, J. P.

AU - Cornil, J.

AU - Brédas, J. L.

N1 - Funding Information: R.A.L. Vallée is grateful to the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (NWO-CW) for supporting this research. The work in Arizona is supported by the National Science Foundation (CHE-0078819), the Petroleum Research Fund, and the IBM Shared University Research Program. The work in Mons is supported by the Belgian Federal Government ‘InterUniversity Attraction Pole in Supramolecular Chemistry and Catalysis (PAI 4/11)’, and the Belgian National Fund for Scientific Research (FNRS-FRFC). J.C. is an FNRS research associate; J.P.C. acknowledges a grant from the Fonds pour la Formation à la Recherche dans l’Industrie et dans l’Agriculture (FRIA).

PY - 2003/4/22

Y1 - 2003/4/22

N2 - The radiative lifetime of single 1,1′-dioctadecyl-3,3,3′, 3′-tetramethylindodicarbocyanine molecules, embedded in a polymer thin film, has been characterized. At room temperature the chemically identical molecules exhibit strong fluctuations in their fluorescence lifetime. The possible conformational origin of these fluctuations has been addressed by semi-empirical quantum-chemical calculations. Specifically, the impact of conformational effects induced by thermal motion on the transition energy and the value of the transition dipole moment has been studied. The results indicate that the strong fluctuations cannot be explained by pure thermally activated conformational changes. Since quenching mechanisms are not responsible for the observed fluctuations, we suggest that molecular segmental dynamics of the surrounding polymer play a key role in determining the lifetime fluctuations.

AB - The radiative lifetime of single 1,1′-dioctadecyl-3,3,3′, 3′-tetramethylindodicarbocyanine molecules, embedded in a polymer thin film, has been characterized. At room temperature the chemically identical molecules exhibit strong fluctuations in their fluorescence lifetime. The possible conformational origin of these fluctuations has been addressed by semi-empirical quantum-chemical calculations. Specifically, the impact of conformational effects induced by thermal motion on the transition energy and the value of the transition dipole moment has been studied. The results indicate that the strong fluctuations cannot be explained by pure thermally activated conformational changes. Since quenching mechanisms are not responsible for the observed fluctuations, we suggest that molecular segmental dynamics of the surrounding polymer play a key role in determining the lifetime fluctuations.

UR - http://www.scopus.com/inward/record.url?scp=0037461159&partnerID=8YFLogxK

U2 - 10.1016/S0009-2614(03)00379-8

DO - 10.1016/S0009-2614(03)00379-8

M3 - Article

AN - SCOPUS:0037461159

SN - 0009-2614

VL - 372

SP - 282

EP - 287

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1-2

ER -

Molecular fluorescence lifetime fluctuations: On the possible role of conformational effects

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this