[Wien] Mixer surprise when using PBE0 hybrid on-site functional

Peter Blaha pblaha at theochem.tuwien.ac.at
Mon Jan 23 07:00:02 CET 2017


Sorry, but I cannot reproduce this.

Starting from a converged GGA+U calculation, -eece converges smoothly, 
keeps the :mmt at 8 uB and a reasonable gap of 1.6 eV and :MV goes to 10-4.

(quick test with few k-points and rkmax only 6.5)

Am 20.01.2017 um 22:16 schrieb Laurence Marks:
> I can provide some partial responses, although there are also some
> things that I don't understand. Some of this (maybe most) is not the
> mixer but in other parts of Wien2k.
>
> First, the old (2008) version is there if you use MSEC1, but I have not
> tested it and it may fail. Better is to use MSEC3 which is almost the
> old version. For some classes of problems this is more stable than MSR1,
> and works better. If you are talking about the pre-multisecant version
> (BROYD) that vanished some time ago.
>
> Second, there is a nasty "feature" particularly for +U (eece) cases,
> which is partially discussed in the mixer Readme. There is no guarantee
> that a solution exists -- the KS theorem is for densities but U is an
> orbital term. It is very possible to have cases where there is no
> fixed-point solution. The older MSEC1 (maybe BROYD) could find a fake
> solution where the density was consistent but the orbital potential was
> not. The latest version is much better in avoiding them and going for
> "real" solutions rather than being trapped. For orbital potentials it is
> very important to look at :MV to check that one really has a
> self-consistent orbital potential.
>
> Third, there are cases where PBE (and all the GGA's in Wien2k that I
> have tested) give unphysical results when applied to isolated d or f
> electrons as done for -eece. I guess that the GGA functionals were not
> designed for the densities of just high L orbitals. This leads to very
> bad behavior of the mixing. I know of no way to solve this in the mixer,
> it is a structural problem. It goes away if LDA is used as the form for
> VXC in -eece.
>
> Fourth, larger problem with low symmetry (P1 in particular) can
> certainly behave badly. Part of this might be "somewhere" in Wien2k
> coding, part of it is generic to a low symmetry problem. In many cases
> these have small eigenvalues in the mixing Jacobian which are removed
> when symmetry is imposed. All one can do is use MSEC3 or some of the
> additional flags (see the mixer README) such as "SLOW".
>
> Fifth...probably exists, but I can't think of it immediately.
>
> On Fri, Jan 20, 2017 at 2:03 PM, Xavier Rocquefelte
> <xavier.rocquefelte at univ-rennes1.fr
> <mailto:xavier.rocquefelte at univ-rennes1.fr>> wrote:
>
>     Dear Colleagues
>
>     I did recently a calculation which has been published long time ago
>     using a old WIEN2k version (in 2008).
>
>     It corresponds to a spin-polarized calculation for the compound CuO. The
>     symmetry is removed and the idea is to estimate the total energies for
>     different magnetic orders to extract magnetic couplings from a mapping
>     analysis. Such calculations were converging fastly without any trouble
>     in 2008.
>
>     Here I have started from the scratch with a case.cif file to generate
>     the case.struct file and initializing the calculation in a standard
>     manner.
>
>     Then I wanted to have the energy related to a ferromagnetic situation
>     (not the more stable). I have 8 copper sites in the unit cell I am
>     using.
>
>     When this calculation is done using PBE+U everything goes fine. However
>     when PBE0 hybrid on-site functional is used we observed oscillations and
>     the magnetic moment disappear, which is definitely not correct. It
>     should be mentionned that the convergency is really bad. If we do a
>     similar calculation on the cristallographic unit cell (2 copper sites
>     only) the calculations converge both in PBE+U and PBE0.
>
>     The convergency problems only arises for low-symmetry and high number of
>     magnetic elements. I didn't have such problems before and I wonder if we
>     could still use old mixer scheme in such situations. Looking at the
>     userguide, it seems that the mixer does not allow to do as before and
>     PRATT mixer is too slow.
>
>     Did you encounter similar difficulties (which were not in older WIEN2k
>     versions)?
>
>     Best Regards
>
>     Xavier
>
>     Here is the case.struct:
>
>     blebleble
>     P   LATTICE,NONEQUIV.ATOMS: 16 1_P1
>     MODE OF CALC=RELA unit=bohr
>       14.167163  6.467777 11.993298 90.000000 95.267000 90.000000
>     ATOM  -1: X=0.87500000 Y=0.75000000 Z=0.87500000
>                MULT= 1          ISPLIT= 8
>     Cu         NPT=  781  R0=0.00005000 RMT=    1.9700   Z: 29.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM  -2: X=0.12500000 Y=0.25000000 Z=0.62500000
>                MULT= 1          ISPLIT= 8
>     Cu         NPT=  781  R0=0.00005000 RMT=    1.9700   Z: 29.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM  -3: X=0.12500000 Y=0.25000000 Z=0.12500000
>                MULT= 1          ISPLIT= 8
>     Cu         NPT=  781  R0=0.00005000 RMT=    1.9700   Z: 29.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM  -4: X=0.87500000 Y=0.75000000 Z=0.37500000
>                MULT= 1          ISPLIT= 8
>     Cu         NPT=  781  R0=0.00005000 RMT=    1.9700   Z: 29.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM  -5: X=0.62500000 Y=0.25000000 Z=0.62500000
>                MULT= 1          ISPLIT= 8
>     Cu         NPT=  781  R0=0.00005000 RMT=    1.9700   Z: 29.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM  -6: X=0.37500000 Y=0.75000000 Z=0.87500000
>                MULT= 1          ISPLIT= 8
>     Cu         NPT=  781  R0=0.00005000 RMT=    1.9700   Z: 29.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM  -7: X=0.37500000 Y=0.75000000 Z=0.37500000
>                MULT= 1          ISPLIT= 8
>     Cu         NPT=  781  R0=0.00005000 RMT=    1.9700   Z: 29.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM  -8: X=0.62500000 Y=0.25000000 Z=0.12500000
>                MULT= 1          ISPLIT= 8
>     Cu         NPT=  781  R0=0.00005000 RMT=    1.9700   Z: 29.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM  -9: X=0.87500000 Y=0.41840000 Z=0.62500000
>                MULT= 1          ISPLIT= 8
>     O          NPT=  781  R0=0.00010000 RMT=    1.6900   Z: 8.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM -10: X=0.12500000 Y=0.91840000 Z=0.87500000
>                MULT= 1          ISPLIT= 8
>     O          NPT=  781  R0=0.00010000 RMT=    1.6900   Z: 8.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM -11: X=0.12500000 Y=0.58160000 Z=0.37500000
>                MULT= 1          ISPLIT= 8
>     O          NPT=  781  R0=0.00010000 RMT=    1.6900   Z: 8.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM -12: X=0.87500000 Y=0.08160000 Z=0.12500000
>                MULT= 1          ISPLIT= 8
>     O          NPT=  781  R0=0.00010000 RMT=    1.6900   Z: 8.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM -13: X=0.62500000 Y=0.58160000 Z=0.87500000
>                MULT= 1          ISPLIT= 8
>     O          NPT=  781  R0=0.00010000 RMT=    1.6900   Z: 8.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM -14: X=0.37500000 Y=0.08160000 Z=0.62500000
>                MULT= 1          ISPLIT= 8
>     O          NPT=  781  R0=0.00010000 RMT=    1.6900   Z: 8.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM -15: X=0.37500000 Y=0.41840000 Z=0.12500000
>                MULT= 1          ISPLIT= 8
>     O          NPT=  781  R0=0.00010000 RMT=    1.6900   Z: 8.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>     ATOM -16: X=0.62500000 Y=0.91840000 Z=0.37500000
>                MULT= 1          ISPLIT= 8
>     O          NPT=  781  R0=0.00010000 RMT=    1.6900   Z: 8.0
>     LOCAL ROT MATRIX:    1.0000000 0.0000000 0.0000000
>                           0.0000000 1.0000000 0.0000000
>                           0.0000000 0.0000000 1.0000000
>         1      NUMBER OF SYMMETRY OPERATIONS
>       1 0 0 0.00000000
>       0 1 0 0.00000000
>       0 0 1 0.00000000
>             1
>
>     _______________________________________________
>     Wien mailing list
>     Wien at zeus.theochem.tuwien.ac.at <mailto:Wien at zeus.theochem.tuwien.ac.at>
>     https://urldefense.proofpoint.com/v2/url?u=http-3A__zeus.theochem.tuwien.ac.at_mailman_listinfo_wien&d=CwICAg&c=yHlS04HhBraes5BQ9ueu5zKhE7rtNXt_d012z2PA6ws&r=U_T4PL6jwANfAy4rnxTj8IUxm818jnvqKFdqWLwmqg0&m=2XKWFhupuwNnAG_KMjoPsmaknSsM7dZHIYk6PeNkTHI&s=e_j2nM5dAAeol3fy52jir16AbaPkAQFlNIRahgZuEvQ&e=
>     <https://urldefense.proofpoint.com/v2/url?u=http-3A__zeus.theochem.tuwien.ac.at_mailman_listinfo_wien&d=CwICAg&c=yHlS04HhBraes5BQ9ueu5zKhE7rtNXt_d012z2PA6ws&r=U_T4PL6jwANfAy4rnxTj8IUxm818jnvqKFdqWLwmqg0&m=2XKWFhupuwNnAG_KMjoPsmaknSsM7dZHIYk6PeNkTHI&s=e_j2nM5dAAeol3fy52jir16AbaPkAQFlNIRahgZuEvQ&e=>
>     SEARCH the MAILING-LIST at:
>     https://urldefense.proofpoint.com/v2/url?u=http-3A__www.mail-2Darchive.com_wien-40zeus.theochem.tuwien.ac.at_index.html&d=CwICAg&c=yHlS04HhBraes5BQ9ueu5zKhE7rtNXt_d012z2PA6ws&r=U_T4PL6jwANfAy4rnxTj8IUxm818jnvqKFdqWLwmqg0&m=2XKWFhupuwNnAG_KMjoPsmaknSsM7dZHIYk6PeNkTHI&s=wt8xEGslBsZBo5wAnOmDWSoJb1h-Ead_WGbqDy456EI&e=
>     <https://urldefense.proofpoint.com/v2/url?u=http-3A__www.mail-2Darchive.com_wien-40zeus.theochem.tuwien.ac.at_index.html&d=CwICAg&c=yHlS04HhBraes5BQ9ueu5zKhE7rtNXt_d012z2PA6ws&r=U_T4PL6jwANfAy4rnxTj8IUxm818jnvqKFdqWLwmqg0&m=2XKWFhupuwNnAG_KMjoPsmaknSsM7dZHIYk6PeNkTHI&s=wt8xEGslBsZBo5wAnOmDWSoJb1h-Ead_WGbqDy456EI&e=>
>
>
>
>
> --
> Professor Laurence Marks
> "Research is to see what everybody else has seen, and to think what
> nobody else has thought", Albert Szent-Gyorgi
> www.numis.northwestern.edu
> <http://www.numis.northwestern.edu> ; Corrosion in 4D:
> MURI4D.numis.northwestern.edu <http://MURI4D.numis.northwestern.edu>
> Partner of the CFW 100% program for gender
> equity, www.cfw.org/100-percent <http://www.cfw.org/100-percent>
> Co-Editor, Acta Cryst A
>
>
> _______________________________________________
> Wien mailing list
> Wien at zeus.theochem.tuwien.ac.at
> http://zeus.theochem.tuwien.ac.at/mailman/listinfo/wien
> SEARCH the MAILING-LIST at:  http://www.mail-archive.com/wien@zeus.theochem.tuwien.ac.at/index.html
>

-- 
--------------------------------------------------------------------------
Peter BLAHA, Inst.f. Materials Chemistry, TU Vienna, A-1060 Vienna
Phone: +43-1-58801-165300             FAX: +43-1-58801-165982
Email: blaha at theochem.tuwien.ac.at    WIEN2k: http://www.wien2k.at
WWW:   http://www.imc.tuwien.ac.at/staff/tc_group_e.php
--------------------------------------------------------------------------


More information about the Wien mailing list