Talk:Marcus theory

Earlier work

Ok, starting in on this article. It needs...

A basic introduction

A developement of marcus theory. I think that I will focus mainly on the graphic depiction of the theory, as it is easier to grasp and perhaps later will put in the thermodynamic development.

A section discussing marcus-hush theory and how it is similar and different from marcus theory. Perhaps introduce the Robin-day classification

A section with links to other prominant theories of electron transfer.

April 9, 2007: Hey -- I'm starting in on work on this page as well. I have a number of good graphs of Marcus theory I'll work on uploading, but will first try to get the basic equations in. Feel free to contact me at m.w.holman@gmail.com with questions

June 8, 2008: Aiming to fix the lack of context here and make this more clear -- let me know if more input is needed -Elmundomike 03:39, 9 June 2008 (UTC) —Preceding unsigned comment added by Elmundomike (talk • contribs)

2008 August 6: I'm concerned by the use of "empirical proof" this should rather be "empirical verification" as proof generally refers to a specific type of mathematical argument. —Preceding unsigned comment added by 196.210.156.204 (talk) 17:46, 6 August 2008 (UTC)

2008 October 27: Changed reference to exothermic reactions to exergonic reactions since the equation refers to free energies. Joe K. —Preceding unsigned comment added by 155.198.28.76 (talk) 17:43, 27 October 2008 (UTC)

Needs explanation on what reorganization energy is and significance (e.g. how biological electron transfer systems try to minimize it to increase electron transfer rate). Example: http://www.chm.bris.ac.uk/motm/caeruloplasmin/copper_proteins/t1.htm —Preceding unsigned comment added by Jimhsu77479 (talk • contribs) 23:53, 15 December 2008 (UTC)

This is one of the best technical pages I've read on wikipedia. Excellent job to whoever put the time into making the beginning explanations coherent and understandable. —Preceding unsigned comment added by Vatassery (talk • contribs) 01:21, 2 February 2009 (UTC)

2019-May-24: Attempting to access the Nobel lecture by Rudolf Marcus, I noticed reference #1 relaying to the very .pdf no longer is correct. Instead, the document may be accessed under an address differing from the one deployed earlier, i.e., now

https://www.nobelprize.org/uploads/2018/06/marcus-lecture.pdf

and suggest that whoever feels most responsible for this entry curates this entry accordingly.

Sign

Hi all. The sign in between lambda and G is minus, or plus? I think it is minus, at least, to be consistent with the diagram. --HappyCamper 01:45, 14 May 2009 (UTC)

$\Delta G$ is defined as Efinal - Einitial - in the figure shown, this implies Delta G is negative. $\lambda$ is always positive and is defined as Efinal(at initial state equilibrium geometry) - Efinal(at final state equilibrium geometry) - therefore the Marcus rate is maximized when the -free energy change is equal to the environmental relaxation (lambda), so it should be a plus. On the other hand if you wrote $\Delta$ which is the exoergicity (i.e. $\Delta =-\Delta G$) then yes it would be a negative. 18.74.1.251 (talk) 16:27, 14 May 2009 (UTC)

OK, I see what you are saying, you're right. The diagram makes it seem as if absolute value $|\Delta G^{\circ }|$ is the quantity of interest, but of course this is wrong. I don't suppose you have an idea for how to fix up the picture? Or perhaps a brief note to emphasize that $\Delta G=E_{f}-E_{i}$ would suffice. Your thoughts, 18? --HappyCamper 16:38, 14 May 2009 (UTC)

Yes, I think just stating the sign convention for free energy change should suffice. 18.74.1.251 (talk) 17:12, 14 May 2009 (UTC)