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  Excess Dynamic Stokes Shift of Molecular Probes in Solution

Sajadi, M., & Ernsting, N. P. (2013). Excess Dynamic Stokes Shift of Molecular Probes in Solution. The Journal of Physical Chemistry B, 117(25), 7675-7684. doi:10.1021/jp400473n.

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 Urheber:
Sajadi, Mohsen1, 2, Autor           
Ernsting, Nikolaus P. 2, Autor
Affiliations:
1Physical Chemistry, Fritz Haber Institute, Max Planck Society, ou_634546              
2Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2, D-12489 Berlin, Germany, ou_persistent22              

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 Zusammenfassung: The solvation dynamics of molecular probes is studied by broad-band fluorescence upconversion. The time-dependent position of the S1 → S0 emission band or of a vibronic line shape is measured with ~80 fs, 10 cm-1 resolution. Polar solutes in acetonitrile and acetone, when excited into S1 with excess vibrational energy, show a dynamic Stokes shift which extends to the red beyond the quasistationary state. Equilibrium is then reached by a slower blue shift on a 10 ps time scale. In methanol, excess vibrational energy as large as ~14 000 cm-1 shows no such effect. Nonpolar solutes exhibit an excess red shift of the emission band in both polar and nonpolar solvents even upon excitation near the vibronic origin. The observed dynamics are discussed in terms of transient heating of the excited chromophore, conformational change, and changes of the molecular cavity size. For solvation studies the optical excitation should be chosen close to the band origin.

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Sprache(n): eng - English
 Datum: 2013-05-292013-01-152013-05-302013-05-302013-06-27
 Publikationsstatus: Erschienen
 Seiten: 10
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/jp400473n
 Art des Abschluß: -

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Titel: The Journal of Physical Chemistry B
Genre der Quelle: Zeitschrift
 Urheber:
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Ort, Verlag, Ausgabe: Washington, D.C. : American Chemical Society
Seiten: - Band / Heft: 117 (25) Artikelnummer: - Start- / Endseite: 7675 - 7684 Identifikator: ISSN: 1520-6106
CoNE: https://pure.mpg.de/cone/journals/resource/1000000000293370_1