A Microscopic Model for the Fluctuations of Local Field and Spontaneous Emission of Single Molecules in Disordered Media
Open accessAbstract
We develop a microscopic model to describe the observed temporal fluctuations of the fluorescence lifetime of single molecules embedded in a polymer at room temperature. The model represents the fluorescent probe and the macromolecular matrix on the sites of a cubic lattice and introduces voids in the matrix to account for its mobility. We generalize Lorentz's approach to dielectrics by considering three domains of electrostatic interaction of the probe molecule with its nanoenvironment: 1) the probe molecule with its elongated shape and its specific polarizability, 2) the first few solvent shells with their discrete structure and their inhomogeneity, 3) the remainder of the solvent at larger distances, treated as a continuous dielectric. The model is validated by comparing its outcome for homogeneous systems with those of existing theories. When realistic inhomogeneities are introduced, the model correctly explains the observed fluctuations of the lifetimes of single molecules. Such a comparison is only possible with single‐molecule observations, which provide a new access to local field effects.
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In the spherical Lorentz cavity approximation, and if the polarizability of the object is not too different from that of the surrounding matrix, the lifetime in a dielectric with index n becomes τ_f(n) = (1/n) (3/(n^2+2))^2 τ_f(1).
“In the approximation of the spherical Lorentz cavity, and if the polarizability of the object is not too different from that of the surrounding matrix (Schuurmans et al 2000, Vallée et al 2005), the lifetime in a dielectric with index n becomes (Imbusch and Kopelman 1981)”
From Single-photon sources (2005) · cites this paper as Vallée et al 2005
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Self-citation
- Authors
- Vallée, R. A. L., Van Der Auweraer, M., De Schryver, F. C., Beljonne, D., & Orrit, M.
- Affiliations
- KU Leuven (BE)
- University of Mons (BE)
- Leiden University (NL)
- Corresponding author
- Vallée, Renaud A. L.
- Venue
- ChemPhysChem
- Publisher
- Wiley
- Published
- 2005-01-07
- Volume
- 6
- Issue
- 1
- Pages
- 81-91
- ISSN
- 1439-4235 (ISSN-L)
- 1439-7641
- OpenAlex
- W2146075684
- Cited by
- 59
- References
- 23
- Citations by year
- 2026: 1 · 2024: 1 · 2020: 1 · 2019: 4 · 2018: 2 · 2017: 2 · 2016: 1 · 2015: 4 · 2014: 5 · 2012: 3
- FWCI
- 3.68
- Type
- journal article
- Language
- en
- Open access
- green
- orbi.umons.ac.be
- Licence
- Locations
- ChemPhysChem (publishedVersion)
- PubMed (publishedVersion)
- ORBi UMONS (submittedVersion, other-oa)
- Funders
- Fonds De La Recherche Scientifique - FNRS
- Fonds Wetenschappelijk Onderzoek
- Topics
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Biophysics › Advanced Fluorescence Microscopy Techniques
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Keywords
- single-molecule fluorescence, local field effects, spontaneous emission, random media, polymer matrix, microscopic model, solvation shell, polarizability, cubic lattice model, voids, inhomogeneous dielectrics
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