[Ifeffit] nonsensical negative values / restrictions

Bruce Ravel bravel at bnl.gov
Fri Jun 16 10:10:38 CDT 2017


Felix,

When you fit your EXAFS data using Artemis + Ifeffit or Larch, you are 
using a Levenberg-Marquardt non-llinear, steepest descent algorithm. The 
fit does kn ow anything /at all/ about what you are trying to do. It 
doesn't know what a sensible value for sigma^2 or any other parameter 
is.  All it knows is that you have data and a model that you are 
throwing at the data.

Armed with data and model, the algorithm optimizes the parameters that 
you have flagged as the variables.  It changes those values until it 
makes the sum of the paths look as much like the data as possible.  It's 
goal is to make the red line look like the blue line.  That's it. That's 
all it does.  That's how sigma^2 can come out as a negative number.

A negative sigma^2 or any other nonsensical parameter doesn't represent 
a failure of Artemis.  It is information that is useful to you, the 
person doing the fit.

A nonsense parameter is trying to tell you about a way that the model 
you have proposed does not represent the data that you have measured. 
And it is a hint about what changes you need to explore in your model to 
more properly represent the data.

An example: suppose you have an unknown oxide phase and you have reason 
to believe it is some sort of highly disordered phase.  Just to pull an 
example out of the air, you might think that your sample is filled with 
FeO(OH) when in fact it is filled with FeO.  FeO(OH) is pretty 
disordered, whereas FeO is rocksalt.  If you run Feff on Feo(OH), you 
will get a spread of paths at several distances for the first shell. 
When you make the fit with the FeO(OH) model, the structural 
contribution to the disorder is MUCH higher than in the actual sample. 
The fit is likely to use a negative sigma^2 to counteract that effect.

That's a simple and contrived "explaining example", but it makes the 
point (I hope).  Artemis didn't fail.  The fit is trying to tell you 
that you assumptions were not realized in the data.

In short, I agree that your results make no sense, but I suggest that 
the problem is that you are making a poor assumption in your fitting model.

It also might be the case that there is a problem with the measurement 
of your data that introduces a systematic error that the fit compensates 
for by applying a weird parameter value.

Or maybe you have a sulfide instead of the oxide you were expecting.

Or maybe you ran Feff for the Pt K edge rather than the Pt L3 edge. 
(Oops! I actually do that with embarrassing frequency....)

Or something else I haven't thought of....

HTH,
B


On 06/16/2017 02:09 AM, Felix E. Feiten wrote:
> Dear all,
> 
> I have the following problem:
> 
> In some fits using Artemis (Demeter 0.9.25) I will get negative values 
> for parameters where it makes no sense at all.
> For example, when trying to fit two first shell paths, Pt-Pt and Pt-O, 
> for a Pt nanoparticle,
> sigma^2 for the Pt-O path becomes negative.
> 
> Obviously, sigma^2 has to be a positive number.
> 
> My questions:
> 
> 1. Why does the fit algorithm do this?
> 
> 2. What can I do to avoid this?
> 
> I know that there are most likely significant problems with my fit if 
> this behaviour occurs.
> As far as I know it's possible to impose restrictions in Artemis and if 
> anyone could point me
> towards a tutorial explaining how to implement restrictions that might 
> be a first step in the right direction.
> Currently, the chapter "Constraints and restraints" in the Artemis 
> documentation is "Coming soon......".
> 
> With kind regards,
> 
> Felix
> 
> 
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-- 
  Bruce Ravel  ------------------------------------ bravel at bnl.gov

  National Institute of Standards and Technology
  Synchrotron Science Group at NSLS-II
  Building 743, Room 114
  Upton NY, 11973

  Homepage:    http://bruceravel.github.io/home/
  Software:    https://github.com/bruceravel
  Demeter:     http://bruceravel.github.io/demeter/


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