14. Prof. Rudolph Marcus - Electron Transfer Theory and Its Evolution (Feb 3, 2022)

Full title: Electron transfer theory and evolution of the theory to treat other quite different processes
Speaker: Prof. Rudolph A. Marcus (California Institute of Technology, USA)

00:00 - Everyone is getting connected
00:30 - Introduction
02:31 - Beginning of the talk
04:14 - Electron transfer reactions
07:00 - Franck-Condon principle
18:28 - Reaction rates and Inverted region
26:20 - Atom transfer reaction and cross-reaction rates
29:59 - Formation of electronically excited products
31:31 - Tafel slopes and Ferrocene/Alkanethiol/Au system
34:06 - Comparing simulations and Marcus theory

35:34 - First Q&A
36:49 - Q1: Limitations of the quadratic equation
41:30 - Q2: Franck-Condon principle and atom transfer
45:40 - Q3: Limitations of Marcus theory

49:38 - Bilayer membrane and photosynthesis
53:34 - ATP synthase: rotary catalysis

1:15:14 - Second Q&A
1:15:39 - Q1: Advice for PhD students
1:20:26 - Q2: The symmetry of the barrier
1:27:05 - Q3: Proton tunnelling in ATPase
1:29:20 - Q4: Opinion about the rise of DFT/MD

https://www.electrochemicalcolloquium...

#theory #chemistry #education

Abstract: 
The theory of electron transfer reactions had its beginning in treating experimental data on the simplest class of reactions in all of chemistry, self-exchange electron transfer reactions. They were studied largely via isotopic tracers, particularly in the 1940s-1960s. Some of this history is described in a recent short article [1]. A central idea of “give and take” in the theory was then extended to other transfer processes, (SN2 reactions, methyl cation transfer reactions) none of them electron transfers, particularly to experimental data on reaction rates and to computational data on reaction energies of activation. In this lecture I describe some of the early history as well as two modern applications of the “give and take”, single molecule kinetic data on chemical-mechanical processes in biological motors, particularly F1 ATPase [2], and the voltage-dependent electrical conductivity of single molecules [3].

1. R. A. Marcus J. Chem. Phys., 153, 210401, doi: 10.1063/5.0035434 (2020)
2. S. Volkan-Kacso and R. A. Marcus Q. Rev. Biophysics., 50 (14), 1-13, doi: 10.1017/S0033583517000129 (2017)
3. J. K. Sowa and R. A. Marcus J. Chem. Phys., 154, 034110, doi: 10.1063/5.0034782 (2021)