Subject: Re: Summary of relationships between IP, EA and electrochemistry

From: Geoff Hutchison <hutchisn{at}chem.northwestern.edu>
Date: Wed, 17 Sep 2003 14:23:06 -0500

Last week, I asked about the relationship between gas-phase IP and EA 
values and electrochemical values. In particular I was trying to 
remember a paper I had read, but could no longer find in my files.

Thanks to Toomas Tamm, Christopher Cramer, Roger DeKock, and Brian 
Peterson for suggestions.

The particular article I remembered was found it in a last desperate 
SciFinder search. It relates IP and EA to electrochemistry by a 
Kamlet-Taft expression and suggests when solvent effects might vary due 
to polarizability:
M. Jonsson, A. Houmam, G. Jocys, and D. D. M. Wayner, J. Chem. Soc., 
Perkin Trans. 2, 1999, 425-429. "Solvent effects on redox properties of 
radical ions"

Several posters suggested the following paper, which discusses 
oxidation potentials and compares semiempirical solvation methods to 
bare gas-phase methods:
P. Winget, E.J. Weber, C.J. Cramer, and D.G. Truhlar, Phys. Chem. Chem. 
Phys., 2000, 2, 1231-1239, "Computational electrochemistry: aqueous 
one-electron oxidation potentials for substituted anilines."

Other suggestions:
Michael Laing, "The electronegativity of a metal and its E0: should
they correlate?", South African Journal of Science, vol 98 (2002), pp
573-580.

You might find what you are looking for in the quantum chemistry 
textbook by
John Lowe, Academic Press, second edition.

----

Original post:
I'm writing up a manuscript and am trying to find a reference I know I
once had that related gas-phase IP and EA values to electrochemistry.
It empirically corrected for solvent effects via a linear relationship
(perhaps a linear free energy relationship?).

In particular, I'm interested in organic pi-conjugated type molecules,
but others could work too.

If anyone has leads on this article or other articles relating
gas-phase IP/EA data to electrochemical measurements, I'd appreciate
it. I'll be glad to summarize to the list.

--
-Geoff Hutchison		<hutchisn{at}chem.northwestern.edu>
Ratner/Marks Groups	(847) 491-3295
Northwestern Chemistry	http://www.chem.northwestern.edu/