[Wien] Top surface layer seems to be isolated from the rest of the system

Peter Blaha pblaha at theochem.tuwien.ac.at
Fri Jun 25 16:19:43 CEST 2021


A W atom could have other formal valencies than 6+ and an electronic 
reconstruction is not impossible (remember the famous LAO/STO interface)

Of course the surface depends a lot on the preparation conditions and on 
the vacuum / O partial pressure, H2O traces (or even "water") ...
There could be several possible surface reconstructions. Thus you can 
try various supercells with W vacancies to reduce the formal 2+ charge) 
or some O on top (but I don't like this "sticking out").
Finally do the thermodynamics and calculate a surface phase diagram as 
function of O partial pressure.

In any case, I hope you have followed what Ludmilla said and use the 
theoretical lattice parameter (just in case- it could be much larger 
with PBE than experiment).

And clear is: if the surface layer lifts off, it is a clear indication 
that your model is very "unrealistic".

Am 25.06.2021 um 14:43 schrieb Laurence Marks:
> Sorry Peter, that is also wrong.
> 
> The valence of a WO2 layer is 2+ ; of the O layer 2-. A valence neutral 
> surface comes from
> a) Adding OH above every W -- 1-
> b) Add 1/2 the O above, and letting the structure relax in a 2x1 cell 
> (or larger) -- the last layer has a valence of 1- per 1x1
> c) Adjusting a top WO2 layer so it has a valence of 1+ per 1x1 (tricky)
> 
> Note: a) is for wet samples (in air); b) more common for dry but only if 
> the top O can adequately bond; c) less common but not impossible. There 
> is some literature, but I expect many of the existing calculations are 
> dodgy.
> 
> _____
> Professor Laurence Marks
> "Research is to see what everybody else has seen, and to think what 
> nobody else has thought", Albert Szent-Györgyi
> www.numis.northwestern.edu <http://www.numis.northwestern.edu>
> 
> On Fri, Jun 25, 2021, 07:16 Peter Blaha <pblaha at theochem.tuwien.ac.at 
> <mailto:pblaha at theochem.tuwien.ac.at>> wrote:
> 
>     Remove the O atoms, which are sticking out of the lower surface.
>     This makes the system inversion symmetric and more realistic.
>     Since you are now not stoichiometric anymore, eventually test with more
>     than 5 layers .
> 
>     Am 25.06.2021 um 13:42 schrieb Dr. K. C. Bhamu:
>      > Dear Prof. L. Marks,
>      > Thanks for your suggestions.  Yes, WO3 is an insulator.
>      >
>      > I am facing the same issue for WC (SG: 187).
>      >
>      > I have worked on Ni(OH)2 and ZnO surfaces and I did not face any
>      > difficulties there. Ni(OH) surface is also polar.
>      >
>      > For the present case, I do not have much choice. I was asked to
>     provide
>      > the absorbance of some molecules on the (100) surface of WO3. The
>      > experimental group is not using any substrate/support for it.
>      >
>      > I will read up on oxide surfaces.
>      >
>      > Thank you very much,
>      > Bhamu
>      >
>      >
>      >
>      >
>      >
>      >
>      >
>      >
>      > On Fri, Jun 25, 2021 at 12:46 PM Laurence Marks
>      > <laurence.marks at gmail.com <mailto:laurence.marks at gmail.com>
>     <mailto:laurence.marks at gmail.com <mailto:laurence.marks at gmail.com>>>
>     wrote:
>      >
>      >     N.B., your cell is polar, and you are not satisfying valence
>      >     neutrality or Pauling's rules. It will never occur in
>     reality, and
>      >     any results you obtain with it will move science backwards.
>      >
>      >     Read up on oxide surfaces, much is known.
>      >
>      >     _____
>      >     Professor Laurence Marks
>      >     "Research is to see what everybody else has seen, and to
>     think what
>      >     nobody else has thought", Albert Szent-Györgyi
>      > http://www.numis.northwestern.edu
>     <http://www.numis.northwestern.edu>
>     <http://www.numis.northwestern.edu <http://www.numis.northwestern.edu>>
>      >
>      >     On Fri, Jun 25, 2021, 01:59 Laurence Marks
>     <laurence.marks at gmail.com <mailto:laurence.marks at gmail.com>
>      >     <mailto:laurence.marks at gmail.com
>     <mailto:laurence.marks at gmail.com>>> wrote:
>      >
>      >         Did you check:
>      >         a) The BVS, to ensure that you do not have a GIGO surface?
>      >         b) Whether the system has a decent gap or not -- I
>     believe WO3
>      >         should be an insulator.
>      >         c) Whether you are satisfying valence neutrality at the
>     surface.
>      >
>      >         I expect you have a GIGO surface, 99.99% probability. You
>     cannot
>      >         just create an oxide supercell and expect it to lead to a
>      >         realistic surface. Fixing layers won't help, and is
>     flawed thinking.
>      >
>      >         GIGO.
>      >
>      >         _____
>      >         Professor Laurence Marks
>      >         "Research is to see what everybody else has seen, and to
>     think
>      >         what nobody else has thought", Albert Szent-Györgyi
>      > http://www.numis.northwestern.edu
>     <http://www.numis.northwestern.edu>
>     <http://www.numis.northwestern.edu <http://www.numis.northwestern.edu>>
>      >
>      >         On Fri, Jun 25, 2021, 01:31 Dr. K. C. Bhamu
>     <kcbhamu85 at gmail.com <mailto:kcbhamu85 at gmail.com>
>      >         <mailto:kcbhamu85 at gmail.com
>     <mailto:kcbhamu85 at gmail.com>>> wrote:
>      >
>      >             Dear Wien2k Users,
>      >
>      >             I am trying to relax the WO3 surface structure (1x1x5
>     with
>      >             15 Ang vacuum). The bulk structure crystallizes in 
>     221 SG.
>      >             Then I created the 1x1x5 layered structure and
>     relaxed the
>      >             top two layers with the bottom three layers kept fixed.
>      >             I see after relaxation, the top layer detached from the
>      >             system (the W-O bond length increased from 1.9 to 2.3
>     Ang),
>      >             you can see from the PDF provided with this email.
>      >             I have tried with QE as well and the same problem I
>     faced there.
>      >             I am wondering if someone has faced a similar
>     experience and
>      >             would like to share his/her experience with me to tackle
>      >             this issue.
>      >
>      >             I have used a different strategy: with U, with U, with
>      >             dipole correction, without dipole correction, vacuum up
>      >             to 30Ang.
>      >
>      >             As the bulk system is a high symmetry system, is it the
>      >             reason due to the symmetry? If so then how one can
>     handle it?
>      >
>      >             I am providing the required information here in the tar
>      >             file  (PLEASE DOWNLOAD FROM HERE
>      >           
>       <https://urldefense.com/v3/__https://we.tl/t-0vedkrUS54__;!!Dq0X2DkFhyF93HkjWTBQKhk!Day7KZQBXQaPn8HGxSpldvOiJzObtS73z_8I17izzlA5ZmuvSj27rMzSsjCo-bt6MCzNAQ$ <https://urldefense.com/v3/__https://we.tl/t-0vedkrUS54__;!!Dq0X2DkFhyF93HkjWTBQKhk!Day7KZQBXQaPn8HGxSpldvOiJzObtS73z_8I17izzlA5ZmuvSj27rMzSsjCo-bt6MCzNAQ$>>).
>      >
>      >             I would appreciate it if someone shares their experience
>      >             with me.
>      >
>      >             Regards
>      >             Bhamu
>      >
>      >
>      >
>      >
>      >
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