Peng, I think what everyone has said is quite useful, but there is likely another aspect to consider as you make revisions. Based on the reviewer comments, it sounds like you are trying to interpret your fitted N values as being statistically distinct. My guess is that is not correct, as Matt suggested, and the fact that the N is lower in fluorescence suggests that overabsorption is attenuating the EXAFS amplitude, as Matthew suggested. If you really want to make the claim of differences in coordination environment then you should also look at R. A lower coordination number should be accompanied by a decrease in R. How R shifts will be impacted by the resolution of the data, determined by your k-range, but I think if fitting a single Sb-O path then in most cases you should see R change if N is truly going down. It can get more complicated, clearly, and the S02 you are using may not be a perfect value, as Shelly's paper indicates, but if N is truly going down in one sample then R definitely should be changing. I do not think about Sb very often, so if the only way for coordination to change is from a change in redox state then you should see a shift in the XANES spectrum. However, be cautious here because overabsorption will increase the intensity of a XANES spectrum for normalized absorbances below 1 and decrease the intensity above 1. If the XANES fine structure features of all samples are the same (in position) but you see what I describe in the overall absorbance, then your fluorescence samples is likely just suffering from overabsorption effects and your N will appear smaller. This gives a lower apparent S02, which is likely what the reviewer is getting at. My sense is that what the reviewer is really criticizing is your interpretations based on differences in fitted N values, which may not be valid. Jeff On 10/2/2021 9:48 AM, Kelly, Shelly D. wrote:

Hi Peng:

It might be helpful to understanding some of Matt's points regarding S02 transferability, Ei and energy resolution by looking at this paper.

Comparison of EXAFS foil spectra from around the world DOI: 10.1088/1742-6596/190/1/012032

Kind regards, Shelly

-----Original Message----- From: Ifeffit On Behalf Of Matthew Marcus Sent: Saturday, October 2, 2021 9:04 AM To:ifeffit@millenia.cars.aps.anl.gov Subject: Re: [Ifeffit] S02 selection from reviewer

Since S02 is a parameter in the description of EXAFS and not of the experiment, it's independent of technique. Overabsorption (misnamed 'self-absorption') can reduce the *measured* amplitude, an effect which can be fudged in analysis by reducing S02. If the sample is truly homogeneous (on the scale of the absorption length), then you can calculate the amount of overabsorption to see if it's significant. However, many kinds of samples, such as concentrated powders mixed with a diluent such as BN, this condition is not met. If the particles are large enough for each to have significant absorption edge jumps, then diluting them in BN doesn't fix the problem. mam

On 10/2/2021 12:49 AM, Peng Liu wrote:

...

Dear IFEFFIT members,

I am sorry to bother you again. I asked about S02 selection for the first major revision. I just received the second revision. The reviewer is not satisfied with one S02 value for all our samples. "

1. I am still not satisfied with selected SO2 value (it is set to 0.85). SO2 is not transferable between different samples and detection methods. It is not possible to use a value obtained from different compound using transmission measurement mode to completely different other compound measured using fluorescence mode. One method to fix SO2 value is to measure diluted solution (to avoid self-absorption) of reference material in fluorescence mode. Other is to use multiple spectra fitting for all samples of interest (e.g. with Sb(V)) measured using fluorescence mode where SO2 parameter is the same for all samples.

At the same time I am confident that CN values 5.6, 7.1 and 6.9 correspond to CN(Sb-O)=6. I suggest reconsidering the SO2 value for measurements in fluorescence mode.

"

We do get the S02 from a similar reference material measured in transmission mode, and our samples were all measured in fluorescence mode. It is not possible to measure the diluted reference material in fluorescence mode in one or two months. If you could give me some suggestions, that would be great.

-- Best Regards,

Peng Liu

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Hi everyone I wonder how much effect on the expt value of S02 comes from background subtraction including previous edges, the energy dependence of the atomic background, and the range of the EXAFS. Theoretically S02 is nut a constant but a spectral average. I’d like to see a careful study with a well defined algorithm that could be compared with theoretical estimates. Thanks. John On Sat, Oct 2, 2021 at 8:47 AM Anatoly Frenkel < anatoly.frenkel@stonybrook.edu> wrote:

I think that the variability of S02 between different samples, detection methods etc. may or may not be a big concern for you if 1) the error bars in the CNs (that you are not reporting) are larger than the difference in their mean values (that you are reporting), and/or 2) larger than the difference between their mean values and the CN=6 that the reviewer is asking about. If yes to either 1) or 2), then the variability in the S02 values for differently prepared samples may cause smaller variation in your best fit values of CN than the error bars reported by your fitting program, and your choice of fixing your S02 to be constant (0.85) may be justified. You need to have a really bad non-uniformity or concentration problem so that your effective S02 changed from the expected 0.85 (assuming it is what a correctly performed measurement would give) to, say, 0.5 or 0.6 is my thought.

Anatoly

On Sat, Oct 2, 2021 at 3:50 AM Peng Liu wrote:

...

Dear IFEFFIT members,

I am sorry to bother you again. I asked about S02 selection for the first major revision. I just received the second revision. The reviewer is not satisfied with one S02 value for all our samples. "

1. I am still not satisfied with selected SO2 value (it is set to 0.85). SO2 is not transferable between different samples and detection methods. It is not possible to use a value obtained from different compound using transmission measurement mode to completely different other compound measured using fluorescence mode. One method to fix SO2 value is to measure diluted solution (to avoid self-absorption) of reference material in fluorescence mode. Other is to use multiple spectra fitting for all samples of interest (e.g. with Sb(V)) measured using fluorescence mode where SO2 parameter is the same for all samples.

At the same time I am confident that CN values 5.6, 7.1 and 6.9 correspond to CN(Sb-O)=6. I suggest reconsidering the SO2 value for measurements in fluorescence mode. "

We do get the S02 from a similar reference material measured in transmission mode, and our samples were all measured in fluorescence mode. It is not possible to measure the diluted reference material in fluorescence mode in one or two months. If you could give me some suggestions, that would be great.

-- Best Regards,

Peng Liu _______________________________________________ Ifeffit mailing list Ifeffit@millenia.cars.aps.anl.gov http://millenia.cars.aps.anl.gov/mailman/listinfo/ifeffit Unsubscribe: http://millenia.cars.aps.anl.gov/mailman/options/ifeffit

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