[Ifeffit] XANES pre-edge vs. edge features

[pushkar shejwalkar]

Dear Aditya,
        Matt has, I think sufficiently explained in details about the
pre-edge and its distinction with main energy jump. If my understanding is
correct, and it is possible that I may be wrong as well, the pre-edge peak,
its appearance shape, intensity and energy value can therefore be used by
organometallic researchers to identify and characterize the specific
geometry as well. e.g. tetrahedral geometry in Fe (II). By theoretical
calculations it is possible to validate such values and thus it is possible
to predict the possible geometry of the metal centre (especially with
metals like Fe, I used it earlier).
I hope this will be helpful as well.
Pushkar

On Mon, Jan 25, 2016 at 11:40 PM, Matt Newville <newville at cars.uchicago.edu>
wrote:

> Aditya,
>
> The distinction between "edge" and "pre-edge" is not very clear, either
> when looking at a single spectrum or even conceptually.
>
> In broad terms, the main edge is at the energy where the unoccupied
> electron levels start - the Fermi energy.   For 1s levels, the transition
> is to p levels (and for Fe K edge, the 4p level).  So, the main edge is at
> the energy of the empty 4p levels.   This the transition as being to an
> atomic level.  In a solid (or liquid), the energy levels above the Fermi
> level are highly delocalized and spread over many (if not all) atoms in the
> systems.  Once you get much above the main edge, it's not very easy to
> assign transitions to identifiable atomic transitions, or even assign a
> good quantum number to them.
>
> Pre-edge features are generally considered to be unoccupied atomic levels
> (that is, still assignable to a particular atom, or at least almost so)
> below the main edge.   For the transition metal K edges (such as Fe), the
> main edge is 1s -> 4p.  But Fe has many unoccupied 3d levels.   For a K
> edge to get to transition to these levels, either you need a quadrupole
> transition  (unlikely, but not impossible), or (more likely) for
> bonding/anti-bonding with ligands (typically oxygen) to mix their
> p-orbitals with the metal d-orbitals.    This hybridization is often called
> a ligand field or crystal field.    It often gives very identifiable (and
> at very predictable energies) peaks below the main edge.    Two and
> sometimes even three peaks can be seen and assigned with ligand field
> terminology.    There's sort of a whole industry built up around these
> peaks for transition metal oxides.
>
> These peaks can "leak" into the main edge, and in some cases (say, Cu1+)
> the classification of "sharp features at the edge" is not very clear.  For
> Fe metal, it's pretty clear that the main edge (derivative at 7110.75 eV, a
> small peak on the main edge around 7112.5 eV) is the 4p level, and the rest
> of the features are actually explainable as EXAFS.
>
> Hopefully, someone will correct anything I got wrong!
>
> --Matt
>
>
>
> On Mon, Jan 25, 2016 at 8:13 AM, Aditya Shivprasad <aps202 at psu.edu> wrote:
>
>> Dear list,
>>
>> I was looking at the XANES standard for Fe foil from Hephaestus and I
>> noticed that there was a small, curved feature at the edge (7112 eV),
>> another inflection point at 7116.4 eV, and then the edge step at around
>> 7131 eV. My question is: why is the feature at 7112 eV considered as the
>> edge and not as a pre-edge feature? Are they due to fundamentally different
>> phenomena? I would like to understand where this type of feature comes from
>> so as to be consistent in the current paper that I am writing. I have
>> attached the standard, just in case.
>>
>> Thanks
>> --
>> Aditya Shivprasad
>>
>> aps202 at psu.edu
>> Ph.D Candidate
>> Nuclear Engineering Department
>> Pennsylvania State University
>>
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-- 
Best Regards,
Pushkar Shejwalkar.
Post-doctoral -Researcher,
Tokyo Engineering University,
Tokyo-to
Japan
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