Hi Jan,
Yes, it can be confusing to select the E0 value for spectra like this. The complication is that we basically use E0 for two purposes: for XANES and normalization, we use it as the energy where absorption starts. In this case, the first derivative at the Cu1+ position is perfectly reasonable. But E0 is also used as the k=0 value for the EXAFS. Here, having E0 on the first sharp edge peak can make the spline harder to fit.
The spline will be easier if you move E0 for the EXAFS up will probably work a little better. The place you chose is fine, though "maximum of a derivative" is not really anything more than "convenient" at this point.
In fact (and to follow up on Shelly's suggestion), I would suggest trying both places. One interpretation of that Cu1+ peak is that it really is the Fermi level, and that dip is just really large negative EXAFS. But trying a first-shell fit with a couple of E0 choices is probably a good idea.
But I would probably not bother to treat that first Cu1+ peak as a "pre-edge peak" that should be isolated from the "real" EXAFS.
But also: Feff tends to pick k=0 values that are a bit higher in energy than where the maximum of the first derivative is found. So the EXAFS fit either has a positive E0 value, or you can move the E0 for k=0 up. I don't recall off-hand, but I can believe that for Cu1+ it really does need to be as high in energy as you picked.
FWIW, this is why Larix allows separate values "E0k" for EXAFS k=0 that can be different from the one used for normalization.
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From: Ifeffit