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Extended Förster Theory of Electronic Energy Transport within Pairs of Reorienting Chromophoric Molecules
Umeå University, Faculty of Science and Technology, Chemistry.
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

An extended Förster theory (EFT), previously derived (L. B.-Å. Johansson et al. J. Chem. Phys., 1996,105) has theoretically been adapted and used in simulations of donor-acceptor energy transfer (DAET), which is a process often referred to as FRET. It was shown that the classical Förster theory is only valid in the initial part of the fluorescence decay. In this thesis an EFT is derived and outlined for electronic energy transport between two fluorescent molecules which are chemically identical, but photophysically non-identical. The energy migration within such asymmetric pairs is partially reversible and therefore referred to as partial donor-donor energy migration (PDDEM). The previously derived model of PDDEM (S. V. Kalinin et al. Spectrochim Acta Part A, 2002,58) is an approximation of the EFT. In particular, the EFT accounts for the time-dependent reorientations as well as the distance that influence the rate of electronic energy migration. The reorientation of the fluorophores transition dipole moments has been simulated using Brownian dynamics. As a result, the related “k2-problem” has been solved. The EFT of PDDEM has also been studied regarding the effect of PDDEM on experimental observables e.g. quantum yield of fluorescence and steady-state anisotropies

Place, publisher, year, edition, pages
Umeå: VMC-KBC , 2009. , 37 p.
Keyword [en]
electronic energy migration/transfer, extended Förster theory, orientation factor, DDEM, PDDEM, time-resolved fluorescence anisotropy, time-correlated single photon counting, Brownian dynamics
Research subject
Physical Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-22471ISBN: 978-91-7264-783-1 (print)OAI: oai:DiVA.org:umu-22471DiVA: diva2:216755
Public defence
2009-06-05, KB3A9, KBC huset, Umeå Universitet, 13:15 (English)
Opponent
Supervisors
Available from: 2009-05-15 Created: 2009-05-11 Last updated: 2009-05-15Bibliographically approved
List of papers
1. On the quantitative molecular analysis of electronic energy transfer within donor–acceptor pairs
Open this publication in new window or tab >>On the quantitative molecular analysis of electronic energy transfer within donor–acceptor pairs
2007 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, Vol. 9, 1941-51 p.Article in journal (Refereed) Published
Abstract [en]

An extended Förster theory (EFT) on electronic energy transfer is presented for the quantitative analysis of time-resolved fluorescence lifetime and depolarisation experiments. The EFT, which was derived from the stochastic Liouville equation, yields microscopic information concerning the reorientation correlation times, the order parameters, as well as inter chromophoric distances. Weakly interacting donor and acceptor groups, which reorient and interact in a pair wise fashion, are considered, under isotropic and anisotropic conditions. For the analysis of experiments it is shown that not only do we need to consider the orientational distributions of the transition dipoles, but the internal reorienting molecular dynamics within the pair which is of even greater importance. The latter determines the shape as well as the rate of the observed donor fluorescence and depolarisation decays, which are most often not mono-exponential functions. It is shown that the commonly used Förster theory is a special case of the EFT. Strategies are presented for applying the EFT, which makes use of Brownian dynamics simulation.

Identifiers
urn:nbn:se:umu:diva-13009 (URN)doi:10.1039/b614817d (DOI)
Available from: 2007-06-26 Created: 2007-06-26 Last updated: 2009-10-28Bibliographically approved
2. Extended Förster theory for determining intraprotein distances: Part III. Partial donor–donor energy migration among reorienting fluorophores
Open this publication in new window or tab >>Extended Förster theory for determining intraprotein distances: Part III. Partial donor–donor energy migration among reorienting fluorophores
2008 (English)In: Physical Chemistry Chemical Physics, Vol. 10, 6962-70 p.Article in journal (Refereed) Published
Abstract [en]

An extended Förster theory (EFT) is derived and outlined for electronic energy migration between two fluorescent molecules which are chemically identical, but photophysically non-identical. These molecules exhibit identical absorption and fluorescence spectra, while their fluorescence lifetimes differ. The latter means that the excitation probability becomes irreversible. Unlike the case of equal lifetimes, which is often referred to as, donor–donor energy migration (DDEM), the observed fluorescence relaxation is then no longer invariant to the energy migration process. To distinguish, the present case is therefore referred to as partial donor–donor energy migration (PDDEM). The EFT of PPDEM is described by a stochastic master equation (SME), which has been derived from the stochastic Liouville equation (SLE) of motion. The SME accounts for the reorienting as well as the translational motions of the interacting chromophores. Synthetic fluorescence lifetime and depolarisation data that mimics time-correlated single photon counting experiments have been generated and re-analysed. The rates of reorientation, as well as the orientational configurations of the interacting D-groups were examined. Moreover the EFT of PPDEM overcomes the classical 2-problem and the frequently applied approximation of 2 = 2/3 in the data analyses. An outline for the analyses of fluorescence lifetime and depolarisation data is also given, which might prove applicable to structural studies of D-labelled macromolecules, e.g. proteins. The EFT presented here brings the analyses of PDDEM data to the same level of molecular detail as that used in ESR- and NMR-spectroscopy.

Identifiers
urn:nbn:se:umu:diva-10693 (URN)doi:10.1039/b810661d (DOI)
Available from: 2008-12-02 Created: 2008-12-02 Last updated: 2011-01-10Bibliographically approved
3. Fluorescence spectroscopic properties analysed within the extended Förster theory with application to Biomacromolecular systems
Open this publication in new window or tab >>Fluorescence spectroscopic properties analysed within the extended Förster theory with application to Biomacromolecular systems
2009 (English)In: Journal of Fluorescence, ISSN 1053-0509, E-ISSN 1573-4994, Vol. 19, no 5, 837-845 p.Article in journal (Refereed) Published
Abstract [en]

The extended Förster theory (EFT) of electronic energy transport accounts for translational and rotational dynamics, which are neglected by the classical Förster theory (FT). EFT has been developed for electronic energy transfer within donor-acceptor pairs [Isaksson, et al, Phys. 16 Chem. Chem. Phys., 9, 1941(2007)] and donor-donor pairs [Johansson, et al, J. Chem. Phys., 105, 10896 (1996); Norlin, et al, Phys. Chem. Chem. Phys., 10, 6962(2008)]. For donors that exhibit different or identical non-exponential fluorescence relaxation within a donor-donor pair, the process of reverberating energy migration is reversible to a higher or lower degree. Here the impact of the EFT has been studied with respect to its influence on fluorescence quantum yields, fluorescence lifetimes as well as depolarisation experiments. The FT predicts relative fluorescence quantum yields which usually agree with the EFT within experimental accuracy, however, substantial deviations occurs in the steady-state and in particular the time-resolved depolarisation data. 

Place, publisher, year, edition, pages
Springer, 2009
Keyword
Electronic energy migration, Homotransfer, Donor-Donor Energy Migration (DDEM), Partial Donor-Donor Energy Migration (PDDEM)
Research subject
Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-22470 (URN)10.1007/s10895-009-0481-z (DOI)
Available from: 2009-05-11 Created: 2009-05-11 Last updated: 2012-08-13Bibliographically approved

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