[Ifeffit] Any coorelation about 'white line" in K-edge XAS with oxidation states?

Robert Gordon ragordon at alumni.sfu.ca
Wed Dec 15 10:07:24 CST 2021


Hi Marco,

As a beginner, you should take a look at some tutorials to get a better 
understanding of what XAFS is:
https://xafs.xrayabsorption.org/tutorials.html
as well as the articles Jia mentioned in his reply. Many synchrotron 
facilities (or universities in partnership with them)
offer introductory courses, with remote participation these days.


A K-edge involves transitions from the core 1s level to what are 
primarily states with p character
    s --> p transition...the s --> d is a pre-edge feature. The white 
line is a s --> p feature for K-edge.

In general, the more electron-withdrawing the ligands, the more the edge 
of the absorbing atom
will shift to higher energy. For an element like Arsenic, correlation 
between white line intensity, edge position
and formal oxidation state (for a given ligand type and arrangement) can 
be seen, but it can be more
complicated.

Type of near-neighbour, number of neighbours, arrangement of neighbours 
can all affect
the near edge as well as the extended region. That is fundamentally why 
XAFS is a useful technique.
Comparison to known compounds is a good first step in identifying what 
is happening with an unknown
sample.

-R.





On 2021-12-15 5:58 a.m., 王茂林 wrote:
>
> Dear Robert:
>
>     Thanks for your such a detailed and quick reply!
>
>     Here I get some points: Because s→d transition is forbidden, we 
> cannot assure that the higher "white line" intensity, the higher the 
> metals' oxidation states are. But we can also get metal's oxidation 
> information via comparation the edge positions and features in 
> spectrum with standard sample (in this case is Ni foil and NiO, 
> the "white line" intensity of NiO is higher, so when the "white line" 
> of spectrum in samples is getting higher, the formal oxidation number 
> is higher). (First we assume that ligands are all oxygen atoms.)
>
>     I'm a beginner of EXAFS, is that right? Thanks again for your 
> patience!
>
>
>
> Marco Wang
>
>
>
>
>
>
>     -----原始郵件-----
>     *發件人:*"Robert Gordon" <ragordon at alumni.sfu.ca>
>     *發送時間:*2021-12-12 12:04:35 (星期日)
>     *收件人:* ifeffit at millenia.cars.aps.anl.gov
>     *抄送:*
>     *主題:* Re: [Ifeffit] Any coorelation about 'white line" in K-edge
>     XAS with oxidation states?
>
>     Hi Marco,
>
>     Yes, a s - d transition is dipole forbidden, but the quadrupole
>     transition can occur, as can a transition
>     s - mixed p/d. The edge position in XAFS for metals like Ni and Cu
>     is taken at the inflection point leading to
>     the first main absorption feature, but is considered to have s - d
>     character. For NiO, features near this edge
>     indicator in the figure would be considered pre-edge. For NiO, the
>     edge position would be considered
>     shifted from that of Ni foil.
>
>     The white line for a K-edge generally corresponds to a noticeable
>     number of unoccupied states with p character
>     on the absorbing atom in the presence of the core hole (i.e.
>     intermediate states) with "small" energy dispersion.
>     Look at the energy difference between the edge indicator and
>     "white line" indicator. That is about 18 eV.
>     For most materials, the work function is 4 - 6 eV between the
>     highest occupied states and the continuum
>     in the ground state. Edge position is sensitive to charge transfer
>     between target atom and ligands, not specifically
>     a formal oxidation state. What you see is not a measurement of the
>     ground state Density of States, but an influence
>     of the core hole on intermediate states, and of the emitted
>     photoelectron during the lifetime of the corehole.
>
>     Much of this terminology also arises from consideration of bulk
>     materials, not nanoscale.
>     Features in the XANES can arise from long range interactions,
>     which are lessened as the scale
>     gets considerably reduced.
>
>     The figure shows a clear transition from something with a
>     pronounced white line feature
>     to something with a less-pronounced feature and increased
>     intensity near the foil edge energy, which I would
>     interpret as a loss of coordinating oxygen yielding something more
>     metallic, or at least more covalent,
>     in character on the substrate. I am curious as to what Ni2Mo3N Ni
>     K-edge would reveal in comparison
>     to their results. It is not unreasonable for the authors to
>     conclude a reduction of the Ni is occurring by loss
>     of coordinating oxygen - "fully reduced to Ni(0)"...well, that is
>     a bit of an overstatement - "extent of electron transfer
>     from the Ni reduced to that of a more metallic/covalent
>     environment" would be more exact, but I understand
>     what is meant and would not argue with another author's writing
>     style if it is not an egregious overstatement.
>
>     So, to answer your question:
>     "how should we correctly interpret the “white line” and edge
>     energy from XAS spectrum of metals’ K-edge and L-edge?"
>
>     We do this by a careful consideration of known standards and
>     knowledge of the influence of bonding
>     environment and extent of electron transfer between absorber and
>     ligands
>
>     The concept of formal oxidation state (oxidation/reduction) is a
>     convenient means of discussing electron
>     transfer in more ionic systems but less useful as the degree of
>     covalency increases.
>
>
>     -R.
>
>
>
>
>
>     On 2021-12-11 6:11 a.m., Marco Wang wrote:
>>
>>     Dear everyone:
>>
>>     Ihave some questions about the interpretation of "white line",
>>     from anarticle (https://doi.org/10.1038/s41467-021-27116-8) and
>>     the figure was attached. In the article, it is said that _“the
>>     sample was fully reduced to Ni (0) state at ~480 °C judging from
>>     the edge position and ‘white-line’ profiles”_.
>>
>>     First, we assumed that the metal wascoordinated with the same anion.
>>
>>     We all know that /K/-edge transition in 3d and 4d metalis' spin
>>     forbidden, so it may be inappropriate to conclude that the
>>     intensity of the "white line" is correlated with metals'
>>     oxidation states. But in otherwords, the probability for s→d
>>     transition may be proportional to thenumber of empty d orbitals,
>>     so it seems likeif the theintensity of "white line" is higher,
>>     the oxidation state is higher.
>>
>>     So, how should we correctly interpret the “white line” and edge
>>     energy from XAS spectrum of metals’ /K/-edge and /L/-edge?
>>
>>
>>
>>     Thank you in advance for your time.
>>
>>     Marco Wang
>>
>>
>>
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>
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