[Ifeffit] Linear combination analysis

Matthew mamarcus at lbl.gov
Thu Jun 5 11:48:34 CDT 2008

MessageOne possibility is over-absorption, which will affect the XANES and EXAFS a bit differently. 
----- Original Message ----- 
  From: Anatoly Frenkel 
  To: 'Ravel, Bruce' ; 'XAFS Analysis using Ifeffit' 
  Sent: Thursday, June 05, 2008 7:58 AM
  Subject: Re: [Ifeffit] Linear combination analysis


  Sounds like a martensitic transition since it depends on the annealing time. Thus, as Bruce wrote, XANES and EXAFS may be expected to be different, due to the different lengths scales - if the boundaries of local fcc regions are small. Another origin of this discrepancy in x and y between XANES and EXAFS fits, is Debye-Waller factor. Due to the extra disorder caused by the interface between fcc and bcc region within the sample, EXAFS in the fcc region in B is not equivalent to EXAFS in D. Analogously, EXAFS in the bcc region in B is not equivalent to EXAFS in A. Therefore, linear combination of A and D will not give you B at "correct" mixing fractions (correct, meaning, real physical mixing fraction). To compensate for that, linear combination problem will stil try to get you the betst fit but by expense of changing the x and y from their "correct" values. 

  XANES is giving you a more accurate result in this sense since Debye-Waller factor, even if different between the unknown (B) from A or D, will not affect XANES that much as EXAFS.


    -----Original Message-----
    From: Ravel, Bruce [mailto:bravel at bnl.gov] 
    Sent: Thursday, June 05, 2008 10:39 AM
    To: XAFS Analysis using Ifeffit
    Subject: Re: [Ifeffit] Linear combination analysis

    Hi Sebastiano,

    > I study a binary alloy (Fe98.7Cu1.3) where a phase change from bcc to fcc
    > is evident (at the Cu K edge of course) and it depends on the annealing
    > time. I have 4 samples A,B,C,D,  where the A shows a perfect bcc structure,
    > while the D a clear fcc structure. B and C have structure that is a mix
    > between the fcc and bcc. I found very interesting to perform some linear
    > fit simulations using the A and D of the XANES and EXAFS of the samples B
    > and C. so  for instance it is possible to get the xanes of the B sample as
    > linear combinations of A and D according to
    > BXANES = x*AXANES+(1-x)*DXANES  and for the EXAFS
    > BEXAFS = y*AEXAFS+(1-y)*DEXAFS
    > The simulations work perfectly but:
    > 1-       Of course I expect that x=y (am I wrong?). but this is not true
    > according to the values that the linear fit provide me. There is a small
    > but significant difference as x=48±2% and y=44±2%. Does this difference
    > have any physical meaning? Is the error a bit too small (so should I
    > increase it?)

    I don't think you are either wrong or right -- it depends upon the
    details of the system.  Were your system a mixture of two powders in
    the ratios you observe in sample B and C, then you would indeed expect

    If I understand your situation correctly, you have an alloy that
    displays a local structure (FCC-like around the Cu atom) that is
    different from the bulk structure (presumably BCC since this is mostly
    Fe).  That means that, on some length scale, the correlations in the
    material change from FCC-like to BCC-like.

    Suppose that length scale at which the correlations change is 10s of
    Angstroms.  That is too far for the EXAFS-with-an-E to see, but near
    the edge the mean free path of the photoelectron might be long enough
    to start seeing that effect.  Thus the structure probed by the XANES
    portion of the spectrum might not, in that sense, be identical to the
    structure probed by the EXAFS.  In that case, you might not expect
    x=y.  The extent of their difference is an indication that the XANES
    is probing the system on a longer length scale than the EXAFS.

    I admit that what I just wrote is a bit half-baked -- it's just my
    initial thought upon reading your email.  But it seems plausible.

    > 2-       For the sample C, I got an amazing simulation adding some noise
    > (0.001), but when I try to export the data (operation: "Write a report") I
    > cannot get the data corrected with the noise (I can get only 6 columns: k,
    > data, fit, residual, sample D, sample A). Is there any way to get the data
    > from the data+noise curve?

    Hmmm... I need to look into the soruce code, but I would guess that I
    just forgot to apply the noise when writing out the LCF fit results.
    I doubt that it will be a difficult fix and I will let the list know
    when I have checked the fix into the SVN repository.  It is unlikely
    that I'll have a chance to make a new Windows executable before
    August, however.

    As a work-around, you could generate a noise spectrum yourself and add
    it to the data outside of Athena.  It won't be the same noise spectrum
    that was used in the fit, but I suspect it'll be hard to tell the
    difference when you make a plot.  As I say in the document "The noise
    is randomly generated using an epsilon that is chosen as a fraction of
    the size of the edge step."


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

     National Institute of Standards and Technology
     Synchrotron Methods Group at NSLS --- Beamlines U7A, X24A, X23A2
     Building 535A
     Upton NY, 11973

     My homepage:    http://xafs.org/BruceRavel
     EXAFS software: http://cars9.uchicago.edu/~ravel/software/exafs/

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