[Wannier] Spin polarized calculations with f-electrons

Mario Burbano burbanom at tcd.ie
Thu Mar 29 11:09:13 CEST 2012


Dear all,


Over the last few months I have been working on doped (Y, Gd, Sm, La, etc)
and reduced ceria systems. My goal is to perform DFT calculations on these
compounds and then extract the ionic forces and dipoles, which I will then
use to fit an interionic potential model. To this end, I wanted to use the
WCs to extract the dipoles. I have carried out this work using mainly
VASP/Wannier90. I also used CPMD (which can output the WCs) in some cases
to check that the results are consistent. My motivation for using
VASP/Wannier90 is the implementation of the Hubbard (U) correction and the
availability of pseudopotentials for lanthanoid elements.


The results I have obtained so far for yttrium-doped CeO2 and
scandium-doped CeO2 have been consistent with each other using either DFT
program. By this I mean that the forces and the dipole moments obtained
from the DFT codes show excellent agreement between them. However, it is
when I carry out simulations with elements that have f-electrons (Ce3+,
Gd3+, Sm3+) that I start having some serious problems. In the case of
Gd-doped ceria, when I visualize the wannier90_centres.xyz file from the
Wannier90 analysis of the data, I can see that the f-electrons that should
have been assigned to Gd, have instead been localized near the nucleus of
the Ce atoms, in addition to the expected 8 valence electrons. I have
encountered similar problems with systems that include reduced cerium
(Ce3+). In this case the single f-electrons from each Ce3+ are assigned to
a single Ce atom (which according to the VASP output should not be
reduced). These wannier centres are conspicuous among the others given that
their spreads are typically higher (>4 Bohr^2) than those of all the other
WCs in the system (2.5 – 3 Bohr^2). In addition, the up and down spin
components from the wannier90 calculation are the same, which, I think, is
unexpected. Finally, a comparison with the results from CPMD is not
available here because CPMD does not have the DFT+U method implemented.


 I am quite confident that the VASP calculations I performed are fine.
Indeed, I have plotted the electronic density of states for said
calculations from VASP and I found them to be in accordance with what would
be expected, i.e. in the case of Gd-doped ceria, the Gd f-states are deep
in the valence band. The calculation also showed charges consistent with Ce
being 4+ and Gd being 3+ and the magnetization of the Gd ions is 7, which
is consistent with the literature.



My question is if there is a specific set of keywords that I need to use
for these f-electron systems. To this end, I attach my wannier90.win,
wannier90.wout, INCAR file from VASP. A plot of the EDOS for Gd-doped ceria
is also available upon request. I would greatly appreciate some help with
this issue.


Mario Burbano

INCAR

SYSTEM = CeO2

Start parameter for this Run:
NWRITE = 2
LPETIM=F write-flag & timer
ISTART = 1 job : 0-new 1-cont 2-samecut
ICHARG = 1

Electronic Relaxation 1
PREC = normal
ENMAX = 500.00 eV Use no more than 400 for hyb
NELM = 150 Or use 150 depending on system
INIWAV = 1 random initial wavefunctions
EDIFF = 1E-05

Ionic Relaxation
EDIFFG = -0.01 stopping-criterion for IOM
NSW = 0 number of steps for IOM
NBLOCK = 1; KBLOCK = 40 inner block and outer block
IBRION = 2 ionic relax: 0-MD 1-quasi-New 2-CG
!POTIM = 0.2
!TEBEG = 1200
ISIF = 2 stress and relaxation
IWAVPR = 1 prediction: 0-non 1-charg 2-wave 3-comb
ISYM = 0 0-nonsym 1-usesym
LCORR = F Harris-correction to forces
ISMEAR = 0
LMAXMIX = 6
!NPAR = 4
ALGO = Normal
LREAL = A
ROPT = 1E-04 1E-04 1E-04
ISPIN = 2
!MAGMOM = 63*0.0 2*7.0 30*0.0
LORBIT = 12
!NBANDS = 576


!LWANNIER90 = .TRUE.
LWANNIER90_RUN = .TRUE.
LWRITE_MMN_AMN   = .TRUE.

LASPH = .TRUE.

LORBIT  =  12

LDAU    =  .TRUE.   DFT+U Parameters
LDAUL   = -1    3    3
LDAUU   =  0    5   7
LDAUJ   =  0    0   0
LMAXMIX =  6
LASPH = .TRUE.

wannier90.win

num_wann = 394
exclude_bands : 395-516
translate_home_cell = T
write_xyz = T
num_iter = 10000
!restart = default
length_unit = bohr
conv_tol = 1E-05
conv_window = 2


use_bloch_phases = T

begin unit_cell_cart
    11.0999000     0.0000000     0.0000000
     0.0000000    11.0999000     0.0000000
     0.0000000     0.0000000    11.0999000
end unit_cell_cart

begin atoms_cart
O        1.0910258     1.5555279     1.1133891
O        1.6168928     1.4308410     6.8344120
O        1.2726312     7.1209920     1.5239751
O        6.7235477     1.3062118     1.5243693
O        6.9849921     1.2755700     7.0070873
O        7.0117723     6.9623947     1.3763876
O        6.9734855     6.8747087     7.0389660
O        1.2816080     4.2024615     1.5141458
O        1.3287112     4.3624672     6.9362300
O        1.2972118     9.4526459     1.3483589
O        1.3706034     9.6482123     6.9524353
O        7.1090675     4.1821279     1.1530493
O        7.1452833     4.1399094     6.6534944
O        6.8159130     9.5397849     1.4425250
O        7.0278822     9.4519766     6.9553476
O        3.8301972     1.6956449     1.5085080
O        4.1800092     1.2534059     6.6640303
O        4.2504328     6.8128734     1.5556019
O        3.9247379     6.7899324     6.9399874
O        9.5556851     1.1386685     1.2527318
O        9.6036212     1.1291998     6.7260156
O        9.5866608     7.0162440     1.2348022
O        9.7441521     6.6994064     6.7313684
O        4.0548661     4.3197004     1.1723938
O        4.1273180     4.3148634     6.8252434
O        4.1772558     9.8811025     1.4115724
O        4.2169280     9.6342031     7.0420338
O        9.7559647     4.2100936     1.2570907
O        9.8481326     4.0300227     6.9914025
O        9.5395371     9.6699812     1.3797357
O        9.7535514     9.5559178     7.0318532
O        1.6712692     1.4300929     4.0238828
O        1.2543316     1.3619023     9.5704645
O        1.4847537     6.7609402     4.3163762
O        1.2548616     6.9356260     9.7869100
O        7.2461518     1.3818800     4.2487517
O        6.7620253     1.5077195     9.8902004
O        7.1182846     7.1713511     4.3022937
O        7.0775316     6.9802018     9.7163932
O        1.3355604     3.9342011     4.1256461
O        1.3149627     4.1328975     9.5825493
O        1.5207152     9.3671966     4.1077831
O        1.2353957     9.4353610     9.7722335
O        6.9859142     4.3444563     3.9066656
O        7.0419841     4.2985905     9.5477929
O        6.9607615     9.9409150     4.4807489
O        6.8498114     9.9006835     9.7935517
O        4.2730595     1.7229243     4.1831688
O        3.9713144     1.4241965     9.7405612
O        4.1850513     6.8978010     4.0957753
O        4.0475432     6.8265599     9.7106643
O       10.0315959     1.3967283     3.8460075
O        9.5551204     1.2485580     9.3996756
O        9.7999703     6.8490059     3.9202658
O        9.6494379     6.9913007     9.6843607
O        4.2028441     4.1931154     4.0845843
O        4.1862072     4.3245559     9.5876039
O        4.1470296     9.7356322     4.3733518
O        4.1740254     9.6720670     9.7716207
O        9.7654108     4.1122673     4.1680258
O        9.7818919     3.9942592     9.7749854
O        9.5273401     9.6357585     4.1431350
O        9.6338072     9.5554361     9.5372859
Gd       5.7302426     2.7687112     2.8334760
Gd      10.9789137    10.9654572     0.0105097
Ce       0.1778309     0.3185873     5.4495023
Ce      11.0260132     5.4730070    11.0700061
Ce      10.9607076     5.5356176     5.4386890
Ce       5.4440578     0.0834043     0.1366895
Ce       5.6382141     0.1742708     5.4959768
Ce       5.4885401     5.5045347     0.0919183
Ce       5.7278683     5.5908857     5.5776579
Ce       2.7531946     2.6635696    11.0489633
Ce       2.7925504     2.9913267     5.4315247
Ce       2.7046285     8.3944282     0.0673516
Ce       2.8253220     8.2792851     5.6985709
Ce       8.2519614     2.7117986    11.0442467
Ce       8.4126651     2.7737429     5.5618419
Ce       8.1952205     8.1584337     0.0519898
Ce       8.3428229     8.4431157     5.6094422
Ce       3.0058818    11.0854546     2.9571521
Ce       2.7320840     0.0080979     8.2708000
Ce       2.9056957     5.4776607     2.7579451
Ce       2.6843252     5.6239897     8.3753906
Ce       8.4102373    11.0299493     2.7425168
Ce       8.2087693    10.9612438     8.3471079
Ce       8.3530073     5.5853908     2.6058968
Ce       8.3022411     5.5315589     8.3088875
Ce      11.0936636     2.8089634     2.6070143
Ce      11.0195643     2.5974887     8.4131393
Ce       0.0012041     8.3390840     2.8207236
Ce       0.0256974     8.3442472     8.3057507
Ce       5.3643603     2.7681623     8.3381502
Ce       5.5863572     8.2839246     2.8753859
Ce       5.5999122     8.4307771     8.3534403
end atoms_cart

mp_grid =     1     1     1

begin kpoints
      0.000000000000      0.000000000000      0.000000000000
end kpoints

Truncated wannier90.wout

  WF centre and spread  315  (  2.955411,  7.977270, -8.320092 )
3.10397663
  WF centre and spread  316  (  1.983168, -7.084571,  3.330386 )
2.82780519
  WF centre and spread  317  (  8.389708, -8.287388,  8.121573 )
3.04872989
  WF centre and spread  318  ( -7.973836,  2.911651,  2.511068 )
3.06077796
  WF centre and spread  319  ( -3.401918,  2.461755,  1.944609 )
2.99807308
  WF centre and spread  320  ( -2.747481, -7.649929,  7.787093 )
3.10885119
  WF centre and spread  321  ( -2.943842,  7.137560, -2.093789 )
2.88281541
  WF centre and spread  322  ( -1.987234, -8.089698, -7.978904 )
3.10697570
  WF centre and spread  323  (  2.773243, -8.264631, -2.946507 )
2.99032824
  WF centre and spread  324  ( -7.568257,  3.066973,  7.682292 )
2.93448218
  WF centre and spread  325  (  2.813919,  8.344642,  3.277612 )
2.91319501
  WF centre and spread  326  ( 10.053932, -5.344354, -4.650336 )
2.47476242
  WF centre and spread  327  (  8.056433, -7.708514, -3.028838 )
3.09028990
  WF centre and spread  328  ( -2.112588,  7.406764,  7.518556 )
2.92660667
  WF centre and spread  329  ( -7.769204, -3.388896,  2.335361 )
2.87424976
  WF centre and spread  330  ( -3.338727,  1.952770, -3.644332 )
2.75161953
  WF centre and spread  331  ( -2.122343,  8.371526,  1.936664 )
2.79772379
  WF centre and spread  332  ( -2.123271,  8.223344,  8.318030 )
2.95807968
  WF centre and spread  333  (  7.649308, -7.742433,  2.587871 )
3.09400540
  WF centre and spread  334  ( -8.553601, -3.383708,  3.220682 )
2.89142249
  WF centre and spread  335  (  2.170253,  7.862902,  8.177933 )
3.01993865
  WF centre and spread  336  ( -8.170698,  2.009430, -8.168123 )
2.87459996
  WF centre and spread  337  ( -3.378961, -3.125420,  2.321571 )
2.97235965
  WF centre and spread  338  (  7.314661,  7.718848,  1.837712 )
2.82518456
  WF centre and spread  339  (  7.601711,  3.611174,  8.276649 )
2.86500869
  WF centre and spread  340  (  8.260864, -2.292446, -2.068143 )
2.98322396
  WF centre and spread  341  (  1.735624,  3.413602,  2.563879 )
2.83866685
  WF centre and spread  342  (  1.996838, -7.902926,  2.514744 )
3.08720409
  WF centre and spread  343  ( -2.013425,  7.984178, -8.201266 )
2.99172689
  WF centre and spread  344  (  7.425085,  8.514192, -7.639445 )
2.93024986
  WF centre and spread  345  (  2.480124, -3.691701,  7.358987 )
2.80989381
  WF centre and spread  346  (  8.017905, -8.470672, -2.185893 )
3.00688507
  WF centre and spread  347  (  8.303022,  8.539391, -8.446310 )
2.95251901
  WF centre and spread  348  ( -8.030027, -8.106592, -2.203690 )
3.06248896
  WF centre and spread  349  (  4.841020,  5.442349,  0.532952 )
2.44329218
  WF centre and spread  350  ( -3.010810, -2.561720, -7.310560 )
2.92096297
  WF centre and spread  351  ( -8.281606, -1.688036,  8.869493 )
2.77204423
  WF centre and spread  352  ( -3.208049,  1.779769, -7.877091 )
2.84982433
  WF centre and spread  353  ( -1.530521,  2.207644,  7.554694 )
2.96087159
  WF centre and spread  354  ( -8.181692,  7.923215,  6.975434 )
2.79038804
  WF centre and spread  355  (  7.982252,  8.693198,  1.757743 )
2.77611846
  WF centre and spread  356  ( -7.291098, -8.247983,  2.951081 )
2.82219938
  WF centre and spread  357  ( -7.448289, -8.447889, -7.259313 )
2.86047293
  WF centre and spread  358  (  3.242955, -8.553512,  7.805895 )
3.03592398
  WF centre and spread  359  ( -2.346036, -8.256709, -2.318301 )
3.06070397
  WF centre and spread  360  ( -2.542093, -3.172905,  7.484967 )
2.90458533
  WF centre and spread  361  (  3.155946, -7.818175,  8.713861 )
3.07195605
  WF centre and spread  362  (  2.895759, -2.745856,  2.889512 )
3.18059131
  WF centre and spread  363  (  2.363604,  2.550049,  2.458465 )
3.30535165
  WF centre and spread  364  ( -3.396423, -3.160862,  8.253963 )
2.80642521
  WF centre and spread  365  (  7.623483,  3.579213,  3.094698 )
2.82291720
  WF centre and spread  366  (  2.111921,  8.714749, -8.232192 )
3.05464852
  WF centre and spread  367  ( -2.083752,  7.098527, -2.888565 )
2.87670157
  WF centre and spread  368  ( -2.512735, -8.164707,  1.935589 )
2.93885801
  WF centre and spread  369  ( -2.080538,  7.957223, -2.080406 )
2.85354471
  WF centre and spread  370  (  2.422977, -7.808186,  7.833933 )
3.10047156
  WF centre and spread  371  (  8.240706,  7.585315,  7.308912 )
2.86138806
  WF centre and spread  372  ( -2.618142, -2.336775,  2.192220 )
2.83746790
  WF centre and spread  373  (  2.017842,  8.321124,  2.425184 )
2.96342095
  WF centre and spread  374  ( -3.338213, -7.343168,  1.909590 )
2.77140536
  WF centre and spread  375  (  2.584014,  3.353781,  1.732777 )
2.85955278
  WF centre and spread  376  (  2.896469,  8.242927, -3.268844 )
2.94442950
  WF centre and spread  377  ( -2.535725, -3.013976,  3.065033 )
3.01193621
  WF centre and spread  378  ( -2.424804, -2.518216, -2.609676 )
2.96225890
  WF centre and spread  379  ( -3.149585, -3.322517, -2.601553 )
3.05900124
  WF centre and spread  380  (  2.822494, -7.100193,  2.435167 )
2.98763778
  WF centre and spread  381  (  3.505806, -6.903623, -8.067028 )
11.46708747
  WF centre and spread  382  ( 10.176170,  5.241469, -5.221244 )
2.42578292
  WF centre and spread  383  (  5.235784, -0.065968, -5.354240 )
3.69196155
  WF centre and spread  384  ( 10.112686,  5.240451, -5.221938 )
2.92049603
  WF centre and spread  385  ( 10.141411,  5.227326, -5.245713 )
2.85520635
  WF centre and spread  386  (  9.722165,  4.820787, -5.230830 )
6.16646019
  WF centre and spread  387  (  1.361169,  0.518060,  9.417393 )
9.99612809
  WF centre and spread  388  ( 10.110982,  5.170869, -5.222982 )
2.96430550
  WF centre and spread  389  ( 10.112519,  5.273404, -5.282557 )
4.20368371
  WF centre and spread  390  (  4.723585, -0.037301, -6.030209 )
9.74295322
  WF centre and spread  391  (  0.392734,  0.529797, 10.290223 )
2.79897493
  WF centre and spread  392  (  0.557381,  0.533053,-10.451580 )
5.65979199
  WF centre and spread  393  (  0.487947,  0.548060, 10.254358 )
4.40782260
  WF centre and spread  394  (  3.062461,  0.220112, -8.035170 )
14.14469343
  Sum of centres and spreads (  2.577830, 49.036143, -1.714244 )
1137.06428007

        Spreads (Bohr^2)       Omega I      =   949.037551765
        ================       Omega D      =     0.000000000
                               Omega OD     =   188.026728302
   Final Spread (Bohr^2)       Omega Total  =  1137.064280067
 ------------------------------------------------------------------------------
  Wannier centres written to file wannier90.up_centres.xyz

 Writing checkpoint file wannier90.up.chk... done

 Time for wannierise         1946.970 (sec)
 Total Execution Time        1947.812 (sec)

 *===========================================================================*
 |                             TIMING
INFORMATION                            |
 *===========================================================================*
 |    Tag                                                Ncalls      Time
(s)|
 |---------------------------------------------------------------------------|
 |kmesh: get                                        :         2
0.013|
 |wann: main                                        :         1
1946.963|
 *---------------------------------------------------------------------------*

 All done: wannier90 exiting
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