[Ifeffit] experimental standard

Anatoly I Frenkel afrenke2 at yu.edu
Tue Nov 18 17:35:35 CST 2014

I think that they study Ga K-edge because Ba L3 and Ti K overlap, hence, those are very difficult to refine in such a complex system.
I also think that if your system is a solid solution (it was not obvious but it is probably what you imply) then the environment of Ga will have a mixture of Ti and Ga somewhere in the r-space and you will have to use a realistic model structure to learn how to do this type of an analysis, not a less sophisticated experimental standard. The latter may likely not even exist, and if it did, it will not be less sophisticated because it will also have a mixture of Ga-Ti and Ga-Ga as your unknown material, hence, the same problem.

I would just make sure it is a solid solution and try to make use of XRD data.
They should tell you if it is an isostructural material to one of the pure components, or a new structure.
If a new structure, and if you can't do Rietveld refinement, then - theory may be the best next step...
If isostructural to something more simple, use that known structure to construct FEFF model.


From: ifeffit-bounces at millenia.cars.aps.anl.gov [ifeffit-bounces at millenia.cars.aps.anl.gov] on behalf of Matthew Marcus [mamarcus at lbl.gov]
Sent: Tuesday, November 18, 2014 6:09 PM
To: XAFS Analysis using Ifeffit
Subject: Re: [Ifeffit] experimental standard

You didn't say what you're trying to find out or even which edge you're doing this at.  That being the case, it's a little hard to know
what the best strategy is.  A few things come to mind:

1.      If you're looking for the environment of the Ga, then obviously, BaO and Ti2O3 aren't terribly useful.  You'd want something
with Ga in an environment similar to that of the unknown.  Is there such a thing as BaGa8Ox with the same structure as BaTi8O16, which
I assume is known?  Another possibility is to use as a reference something in which instead of Ga as the central atom, you have something
nearby in the periodic table, but in a similar environment.  Ga2O3 would only be useful if all you're after is Ga-O and maybe Ga-Ga distances.
Check for other, known oxides in the Ba-Ti-Ga-O system or at least Ba-Ga-O or Ti-Ga-O.

2.      If you're after what the Ga does to the environment of the major elements, then perhaps you could use BaTi8O16 (if that exists)or
barium titanate.  These would give you the Ba-O, Ti-O, and (Ba,Ti)-(Ba,Ti) paths.  My intuitive guess is that if x is small, then you'd be looking
for small changes, so the best standard of all is the x=0 material, if it exists.  Fit that, then add in (Ba,Ti)-Ga paths as appropriate and let
the other paths change and see what happens for x >0.

3.      Is the doped material available as a single crystal?  Has the structure been solved?  Perhaps that information could be used to constrain
the structure.

4.      The stoichiometry you give, Ba(Ti,Ga)8O16, requires the (Ti,Ga) to be in a mixed-valent state (assuming Ba=2, average = 30/8 = 15/4 = 3.75).
That being the case, I'm guessing that the Ga substitutes for the Ti3+, either shifting the average valence so that O isn't 16 anymore or just
replacing the Ti3+ until you've replaced it all.  Either way, Ti XANES would be informative.   There are many papers about the interpretation
of Ti K-edge XANES.

5.      If my guess about Ga substituting only for Ti3+ is correct, *and* you quoted the correct stoichiometry, then,
        a)      Something should happen for x>2 because you can't get an average valence of 3.75 anymore.
        b)      If the Ti3+ and Ti4+ sites are different enough, say octahedral+tetrahedral, then the Ga EXAFS should look like
                that of the Ti3+ only.
        c)      Ga3+ is slightly smaller than Ti3+, so you might see a small contraction around the Ga relative to the Ti.

Good luck.

On 11/18/2014 2:32 PM, Yun Xu wrote:
> Hi all
> I have a complex oxide BaTi8-xGaxO16. What standards I should run?
> Ga is the dopant. I guess I should run the sample without dopant BaTi8O16 as standard, or the simple oxide as BaO, TiO2 Ga2O3?  or is the standard necessary?
> Also, I have colleage working on DFT, I assume the theoretical standard is the result from the DFT calculation, and by using the coordinates of the atoms, I can run FEFF and fit the data.
> Thanks
> Yun
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