Photoinduced Electron Transfer - The Semi-Classical Marcus-Levich-Jortner Theory. RE-EDIT - RMW, UvA

This is a Re-edited and Shortened lecture at the MSc level for chemistry students that are interested in molecular photochemistry.
A very short road from Arrhenius to Marcus to the Franck Condon Weighted Density of States in the Marcus Inverted Region. Learning objectives:

• The Arrhenius equation and the Classical Marcus equation have the same foundations.
• In the Semi-Classical Marcus equation the pre-exponential factor only contains the solvent reorganization energy. The exponential term incorporates a specific vibration that mediates the electron transfer and is important for the vibronic coupling.
• Molecular vibrations can mix into electronic transitions, thereby playing an important role in transfer processes.

• Photochemistry has a direct link with quantum chemistry.
• Intermolecular (or interchromophoric) interactions in the excited state can lead to electronic interactions enabling transfer processes.


For more information see:
Electron Transfer Reactions in Chemistry: Theory and Experiment (Nobel Lecture)†
Prof. Dr. Rudolph A. Marcus
https://doi.org/10.1002/anie.199311113



NEW ADDITION: 15-05-2024
For some mathematical modules on these topics that are freely available see:
https://demonstrations.wolfram.com/au...
(you need the free Wolfram Player, than you can use it).



Electron Transfer Assisted by Vibronic Coupling from Multiple Modes,
(the nice pictures of vibronic coupling in inverted region)
https://doi.org/10.1021/acs.jctc.7b00513


Contemporary Issues in Electron Transfer Research

https://doi.org/10.1021/jp9605663



Jacques E. Moser:
http://photochemistry.epfl.ch/PC/PC2_...

http://photochemistry.epfl.ch/PC/PC2_...


Introduction to Electron Transfer, René M Williams
https://doi.org/10.13140/RG.2.2.16547...



NEW ADDITION: 18-08-2021:
Papers that report oscillations in the Bell shaped Marcus curve
(resonance type effects in Franck-Condon Factor):

Sarai 1979:
https://doi.org/10.1016/0009-2614(79)...
Miller 1984:
https://doi.org/10.1021/ja00330a004
Gunner 1986:
https://doi.org/10.1021/j100407a054
Rujkorakarn 2009:
https://doi.org/10.1016/j.jmgm.2008.0....
Unger 2017:
https://doi.org/10.1021/acs.jpcc.7b09213
Parson 2020:
https://doi.org/10.1063/5.0007569



ADDITION

10-10-2021:
The more commonly used way to call it is: Semi-Classical Marcus-Levich-Jortner Theory
(not Semi-Classical Marcus-Jortner-Levich Theory, although we can encounter both)


QUIZ 1: Are these oscillations at very low Delta G values real or an artifact of the Semi-Classical Marcus theory?


QUIZ 2: How many vibrations in a molecule can mediate the electron transfer efficiently?



Semi Classical Marcus Re Edit