FWF - Magnetic field effect - Magnetic field effects subject to specific solvation

Project: Research project

Project Details


Magnetic field effects on yields of chemical reactions are well documented in the scientific literature. Many of
these effects can be attributed to the radical pair mechanism, i.e. the coherent interconversion of the overall singlet
ant the triplet state in transient, diffusively separated radical ion pairs. It has been postulated, that specific solvation
is at the root of the exceptionally large field effects observed in binary solvent mixtures composed of compounds of
significantly different polarity. In particular, in analogy to the situation in micelles, the enhanced magnetic field
effects have been attributed a prolonged lifetime of the radical ion pair and an increased efficiency of charge
separation. However, only indirect evidence has been put forward, and the effect of the micro-heterogeneity on the
diffusive trajectories of the pair has never been observed directly.
This project focuses on magnetic field effects due to the radical pair mechanism in simple organic model systems in
constrained (micro-heterogeneous binary mixtures) as well as homogeneous environments (neat solvents and
homogeneous solvent mixtures). The model systems (e.g. pyrene/N,Ndimethylaniline, anthracene/N,N-
dimethylaniline, 9,10-dimethylanthracene/1,3-benzenedicarbonitrile, and others) are characterized by the fact that
they form emissive exciplexes, which serve as a sensitive probe of the underlying radical pair dynamics. This
allows the subtle interplay between diffusion and spin evolution to be studied systematically. While steady-state
fluorescence measurements have frequently been applied to these systems, time resolved measurements by the
single photon counting or the frequency resolved modulation technique have not yet been applied systematically in
the presence of an external magnetic field. We propose to devise a time-resolved magnetic field effect
spectrometer, which will allow us to eventually discern the peculiarities of micro-heterogeneous solvent systems in
particular and confined media in general.
Our experimental efforts are accompanied by model calculations that take the stochastic Liouville-von Neumann
equation beyond the low-viscosity approximation as the starting point. The theoretical approach is sufficiently
general to also accommodate biomimetic environments as micelles. By comprehensively investigating these
systems by both experiment and model calculations, we hope to shed light on the parallels and differences between
restricted and freely diffusing systems. Our aim is to find objective criteria when exceptionally large magnetic
fields are to be observed for unlinked, charged radical pairs.
Effective start/end date1/07/0930/06/14


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