[Ifeffit] Reduced chi square values versus F-tests for second shell fits

Bruce Ravel bravel at bnl.gov
Thu Mar 21 17:27:57 CDT 2013

In another message in that thread, Matt calls that "a reasonable way
to start" and makes the valid point that small details can "often get
lost in the fit to the more dominant features of the spectra."

What I am saying is that the reasson that small details "often get
lost" is because there are correlations in any data.  If you fix one
part of the fit and float another part, you have made a very specific
decision to ignore an entire set of correlations.  That may make the
results on those small details much more *precise*, but it most
certainly does not guarantee that the results will be more *accurate*.

So yes, you can do what you want to do.  I said the same in my last
email.  But you have to be prepared to defend against the completely
valid criticism that doing so arbitrarily removes correlations from
the fitting model.  That can have an impact on the accuracy of your
result.  Neither the RCS nor the F test address that problem.

Of course, if you dig through all the stuff that I have written over
the years, I frequently report (in the case of publications) or
recommend (in the case of teaching material) doing things that fall
into the category of improving precision while risking accuracy.
Indeed, any use of constraints in Artemis could engender this
criticism -- and I gas on and on and on about the virtues of
constraints whenever I do EXAFS training courses.  But I always try to
emphasize the importance of honestly assessing the consequences of
these actions, both with myself and with my readership.  As an
example, in http://dx.doi.org/10.1016/j.radphyschem.2009.05.024 I
spend a rather long paragraph clearly stating the most egregious
approximations I made in the analysis presented in that paper.  The
remainder of the paper justifies all that using both the XANES and
other published work on the system.

I guess that none of that answered your specific question about the
nominal disagreement between the RCS and the F test.  I might be
exposing a weakness in my own understanding of the F test right now,
but I can suggest something to think about.  The F test result may be
saying something about the normality of the parameters that you
actually used in the fit.  Try varying some of the procedural
parameters of the fit.  For example, try limiting or expanding the
ranges in k or R by a bit; try different k-weightings; try adding a
bit of artificial noise to your chi(k) data -- anything that slightly
changes the conditions of the fit without actually changing the
details of the model or information content of the data.  Doing so
might help clarify what is going on with your statistical tests.


On Thursday, March 21, 2013 02:38:22 PM Matt Siebecker wrote:
> Hello Bruce,
> Thanks for your response.  By “second shell fits” I mean that the best
> values for the first shell were fitted then fixed and then the fitting
> R-range was moved to the second shell. Similarly to how Matt Newville
> describes here:
> http://millenia.cars.aps.anl.gov/pipermail/ifeffit/2009-April/008779.html
> He describes this as an acceptable approach, although, others in
> the thread disagree.
> Essentially, my question is why
> do the F-test and the RCS results not agree with each other?  The F-test
> indicates model 2 may not be a statistical improvement over model 1 while
> the RCS values show that model 2 is definitely an improvement over model
> 1.  If I consider a reduction in the RCS value of >2x as significant, then
> I would pick model 2.
> However, can I apply this logic when fitting the second shell with
> the best parameters for the first shell fixed and the R-ranges over the
> second shell?
> Thank you again,
> Matt S


 Bruce Ravel  ------------------------------------ bravel at bnl.gov

 National Institute of Standards and Technology
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