Energy transfer processes in the framework of macroscopic quantum electrodynamics

Abstract: Macroscopic bodies, such as surfaces, cavities or surrounding liquids and gasses, can significantly influence and thus control microscopic processes.
A suitable framework to describe these effects is given by macroscopic quantum electrodynamics (QED).
Inspired by the success of this theory applied to the so-called resonance energy transfer (RET), in this thesis the existing theory is on the one hand extended to related but more exotic processes and systems, and on the other hand extended to deal with collective effects and incoherent dynamics.
The work is divided into three main parts.


In the first part, we investigate the competition between interatomic Coulombic decay and Auger decay and how one can change the relation of their rates to each other through their macroscopic environment, such as surfaces or cavities.
In doing so, we develop a new approximate model for Auger decay that allows the dipole approximation and provides a closed-form expression for the Auger decay rate that depends on tabulated atomic data.
It is shown how even a simple dielectric surface can significantly affect the competition between the two rates.
The analysis is kept as general as possible, and analytical expressions are provided that can be applied to arbitrary macroscopic environment well described by its classical Green's tensor.

In the second part of this thesis, we extend the theory of RET in the framework of macroscopic QED to chiral molecules. Chiral molecules are optically active and may interact with the electromagnetic field via their magnetic transition dipole moment in addition to their electric one.
As a result, new channels in the process of RET open up.
The interference of some of these channels is then sensitive to the handedness of the chiral molecules: the RET rate differs between opposite-handed enantiomers and same-handed enantiomers.
This makes RET a candidate for the development of a chiral discrimination technique.
We show how the originally weak discriminatory power of the process can be significantly enhanced by immersing the system in a solvent.
We offer a detailed discussion of a large parameter space for dielectric solvents.
The importance of local-field effects is discussed and appropriate corrections are included in the calculation.
We derive the local-field corrections for chiral solvents that turn out to be much more complex than those for magneto-electric media.
We predict that due to these local-field effects the direction of the discrimination can be inverted inside chiral media depending on the intermolecular distance.
As an opposite limit to the case of a continuous and dense macroscopic solvent, we consider possibly chiral particles surrounding the molecules undergoing RET.
We show that even a single mediating particle can have a significant impact on the discrimination depending on its position.


In the last part of the thesis, we develop a new perturbation scheme based on the master equation of the reduced atomic system in the Markov approximation and additionally extend Fermi's golden rule to density matrices.
We demonstrate the applicability of Fermi's golden rule to density matrices by studying superradiant RET as a function of the initial entanglement in a collectively excited atomic pair.
The new perturbation scheme modifies the splitting between perturbation and bare evolution, such that the bare evolution describes additionally incoherent dynamics such as decays.
The scheme can then be used, for example, to deal with poles in the frequency domain, which are common when using perturbation theory, by a formally rigorous method

Object Details

• Location: Deutsche Nationalbibliothek Frankfurt am Main
• Extent: Online-Ressource
• Language: Englisch
• Notes: Universität Freiburg, Dissertation, 2023

Classification and Topics

• Keyword: Quantenelektrodynamik ; Fluoreszenz-Resonanz-Energie-Transfer ; Quantenelektrodynamik ; Chirale Verbindungen

Contributors, Places and Time

• Event: Veröffentlichung
• (where): Freiburg
• (who): Universität
• (when): 2023
• Creator: Franz, Janine
• Contributor: Buhmann, Stefan Yoshi ; Grant, Edward R. ; Buhmann, Stefan Yoshi ; Dzubiella, Joachim ; Albert-Ludwigs-Universität Freiburg. Physikalisches Institut ; Albert-Ludwigs-Universität Freiburg. Fakultät für Mathematik und Physik

Further information

• DOI: 10.6094/UNIFR/239020
• URN: urn:nbn:de:bsz:25-freidok-2390208
• Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
• Last update: 03.04.2025, 3:57 PM CEST