[CP2K-user] [CP2K:12117] Convergence of hybrid functional calculations

Thomas Kühne tku... at gmail.com
Wed Aug 21 18:15:38 UTC 2019


Dear Xiaoming, 

beside the comments made I would like to add that the excessive usage of OUTER_LOOP 
is not always a good idea. Re-preconditioning with an already well converged WF may also 
lead to the behavior you observed, which is even more pronounced when diagonalization 
based preconditions are employed. 
In your case you may try to use the converged PBE-WF without OUTER_LOOP, or to 
restart from the initial guess with MAX_SCF of the inner loop set between 25-50 steps. 

Cheers, 
Thomas

> Am 21.08.2019 um 17:12 schrieb hut... at chem.uzh.ch:
> 
> Hi
> 
> looks to me to be a problem of numerical accuracy.
> My first try would be to decrease EPS_SCHWARZ.
> 
> regards
> 
> Juerg
> --------------------------------------------------------------
> Juerg Hutter                         Phone : ++41 44 635 4491
> Institut für Chemie C                FAX   : ++41 44 635 6838
> Universität Zürich                   E-mail: hut... at chem.uzh.ch
> Winterthurerstrasse 190
> CH-8057 Zürich, Switzerland
> ---------------------------------------------------------------
> 
> -----cp... at googlegroups.com wrote: -----
> To: "cp2k" <cp... at googlegroups.com>
> From: "Xiaoming Wang" 
> Sent by: cp... at googlegroups.com
> Date: 08/21/2019 04:55PM
> Subject: [CP2K:12115] Convergence of hybrid functional calculations
> 
> Hello,
> 
> I'm trying to calculated the triplet excited state of NaCl (periodic) with PBE0. Before doing
> that I first converged it with PBE, which was very easy for the convergence. Then I
> turned on PBE0 which reads the PBE converged wfn. At the first few steps, the 
> energy change did get reduced but then it increased and the SCF became unstable.
> I played with the parameter linesearch, but it didn't help. Could anyone please
> give me some suggestions? Note that the ground state is fine with PBE0.
> 
> 
> Here is my input:
> -------------------------------------
> &GLOBAL
>  PROJECT_NAME NaCl
>  RUN_TYPE GEO_OPT
>  PRINT_LEVEL MEDIUM
> &END GLOBAL
> &FORCE_EVAL
>  METHOD QS
>  &DFT
>    BASIS_SET_FILE_NAME GTH_BASIS_SETS
>    POTENTIAL_FILE_NAME GTH_POTENTIALS
>    WFN_RESTART_FILE_NAME NaCl-RESTART.wfn
>    UKS
>    MULTIP 3
>    &QS
>       EPS_PGF_ORB 1.0e-12
>    &END
>    &MGRID
>      CUTOFF 1400
>      REL_CUTOFF 40
>    &END MGRID
>    &XC
>      &XC_FUNCTIONAL PBE
>        &PBE
>         SCALE_X 0.564
>         SCALE_C 1.0
>        &END
>      &END XC_FUNCTIONAL
>      &HF
>        FRACTION 0.436
>        &MEMORY
>          MAX_MEMORY 2600
>        &END
>        &SCREENING
>          EPS_SCHWARZ 1.0e-6
>          SCREEN_ON_INITIAL_P TRUE
>        &END
>        &INTERACTION_POTENTIAL
>          POTENTIAL_TYPE TRUNCATED
>          CUTOFF_RADIUS 6.0
>          T_C_G_DATA t_c_g.dat
>        &END
>      &END
>    &END XC
>    &SCF
>      MAX_SCF 20
>      EPS_SCF 1.0e-6
>      SCF_GUESS RESTART
>      &OT
>       ROTATION
>       PRECONDITIONER FULL_KINETIC
>       ENERGY_GAP 0.001
>      &END OT
>      &OUTER_SCF
>       EPS_SCF 1.0e-6
>       MAX_SCF 30
>      &END OUTER_SCF
>    &END SCF
>  &END DFT
>  &SUBSYS
>   &CELL
>      ABC [angstrom] 16.92 16.92 16.92
>      ALPHA_BETA_GAMMA [deg] 90 90 90
>      PERIODIC XYZ
>      SYMMETRY CUBIC
>    &END CELL
>    &TOPOLOGY
>     COORD_FILE_FORMAT XYZ
>     COORD_FILE_NAME nacl.xyz
>    &END TOPOLOGY
>    &KIND Na
>      ELEMENT Na
>      BASIS_SET DZVP-GTH
>      POTENTIAL GTH-PBE-q9
>    &END KIND
>    &KIND Cl
>      ELEMENT Cl
>      BASIS_SET DZVP-GTH
>      POTENTIAL GTH-PBE-q7
>    &END KIND
>  &END SUBSYS
> &END FORCE_EVAL
> --------------------------------------
> 
> 
> The output looks like:
> 
>  ----------------------------------- OT ---------------------------------------
>  ----------------------------------- OT ---------------------------------------
>     1 OT CG       0.15E+00  481.3     0.00112441     -6724.7524787206 -6.72E+03
>     2 OT LS       0.10E+00   10.7                    -6724.8822106857
>     3 OT CG       0.10E+00    9.5     0.00050715     -6724.9031842435 -1.51E-01
>     4 OT LS       0.19E+00    8.7                    -6724.9536990492
>     5 OT CG       0.19E+00    9.4     0.00037942     -6724.9681273512 -6.49E-02
>     6 OT LS       0.99E-01    8.8                    -6724.9693724201
>     7 OT CG       0.99E-01   10.4     0.00020992     -6724.9865892317 -1.85E-02
>     8 OT LS       0.13E+00    8.8                    -6724.9935640889
>     9 OT CG       0.13E+00    9.4     0.00014250     -6724.9940187729 -7.43E-03
>    10 OT LS       0.95E-01    8.7                    -6724.9960612217
>    11 OT CG       0.95E-01    9.3     0.00006184     -6724.9964317459 -2.41E-03
>    12 OT LS       0.12E+00    8.6                    -6724.9969767721
>    13 OT CG       0.12E+00    9.3     0.00003237     -6724.9969977602 -5.66E-04
>    14 OT LS       0.10E+00    8.6                    -6724.9971327130
>    15 OT CG       0.10E+00   11.9     0.00001849     -6724.9971350991 -1.37E-04
>    16 OT LS       0.79E-01    8.6                    -6724.9971656124
>    17 OT CG       0.79E-01    9.6     0.00001222     -6724.9971690250 -3.39E-05
>    18 OT LS       0.89E-01    8.6                    -6724.9971855970
>    19 OT CG       0.89E-01    9.9     0.00000761     -6724.9971858334 -1.68E-05
>    20 OT LS       0.10E+00    9.0                    -6724.9971931351
>  ----------------------------------- OT ---------------------------------------
>  ----------------------------------- OT ---------------------------------------
>     1 OT CG       0.15E+00   19.9     0.00000498     -6724.9971932398 -7.41E-06
>     2 OT LS       0.82E-01    8.6                    -6724.9971940802
>     3 OT CG       0.82E-01   10.4     0.00000357     -6724.9971958172 -2.58E-06
>     4 OT LS       0.14E+00    8.7                    -6724.9971976975
>     5 OT CG       0.14E+00    9.3     0.00000335     -6724.9971981030 -2.29E-06
>     6 OT LS       0.12E+00    8.6                    -6724.9971997017
>     7 OT CG       0.12E+00    9.3     0.00000370     -6724.9971997739 -1.67E-06
>     8 OT LS       0.20E+00    8.6                    -6724.9972026529
>     9 OT CG       0.20E+00    9.3     0.00000494     -6724.9972032479 -3.47E-06
>    10 OT LS       0.80E+00    8.8                    -6724.9972140706
>    11 OT CG       0.80E+00    9.4     0.00002733     -6724.9972231506 -1.99E-05
>    12 OT LS       0.80E-02    8.6                    -6719.9157164774
>    13 OT CG       0.80E-02    9.9     0.00003368     -6724.9972303521 -7.20E-06
>    14 OT LS       0.32E-01    9.2                    -6724.9972548138
>    15 OT CG       0.32E-01   11.2     0.00003227     -6724.9973282204 -9.79E-05
>    16 OT LS       0.13E+00    9.1                    -6724.9974072677
>    17 OT CG       0.13E+00    9.5     0.00003061     -6724.9975608855 -2.33E-04
>    18 OT LS       0.51E+00    8.6                    -6724.9978925811
>    19 OT CG       0.51E+00    9.6     0.00011176     -6724.9983575397 -7.97E-04
>    20 OT LS       0.51E-02    8.6                    -6721.4964318477
>  ----------------------------------- OT ---------------------------------------
>  ----------------------------------- OT ---------------------------------------
>     1 OT CG       0.15E+00   20.9     0.00011858     -6724.9985172669 -1.60E-04
>     2 OT LS       0.58E-01   11.2                    -6724.9970073738
>     3 OT CG       0.58E-01   10.4     0.00007331     -6724.9995517536 -1.03E-03
>     4 OT LS       0.23E+00    8.6                    -6725.0003094891
>     5 OT CG       0.23E+00    9.4     0.00015204     -6725.0023016465 -2.75E-03
>     6 OT LS       0.93E+00    9.5                    -6725.0650303038
>     7 OT CG       0.93E+00    9.4     0.02493217     -6725.3018557157 -3.00E-01
>     8 OT LS       0.10E+00    8.9                    -1644.0225625088
>     9 OT CG       0.10E+00    9.6     0.92198116     -6517.7744998942  2.08E+02
>    10 OT LS       0.51E-01    8.9                    19923.6570264501
>    11 OT CG       0.51E-01    9.4    15.11620648     19207.4345007054  2.57E+04
>    12 OT LS       0.26E-01    8.8                    -7017.2896076309
>    13 OT CG       0.26E-01    9.6     4.17007861      4801.8591626626 -1.44E+04
>    14 OT LS       0.13E-01    8.7                     2811.8906869280
>    15 OT CG       0.13E-01    9.8     3.07766039     -3579.5472107880 -8.38E+03
>    16 OT LS       0.65E-02    8.7                    -4615.7291252627
>    17 OT CG       0.65E-02    9.4     4.95384759    -11738.7814456775 -8.16E+03
>    18 OT LS       0.31E-02    8.7                      261.6526649662
>    19 OT CG       0.31E-02    9.8     3.45312508     -3253.3909721757  8.49E+03
>    20 OT LS       0.17E-02    8.8                   -13571.9973535297
>  ----------------------------------- OT ---------------------------------------
>  ----------------------------------- OT ---------------------------------------
>     1 OT CG       0.15E+00   19.1    11.57459733    -10059.0070566359 -6.81E+03
>     2 OT LS       0.75E-01    8.9                     9274.4374295033
>     3 OT CG       0.75E-01    9.8     8.16592421      5288.7904699808  1.53E+04
>     4 OT LS       0.37E-01    8.7                    12320.0027679343
>     5 OT CG       0.37E-01    9.7    13.27037877      9266.8771057051  3.98E+03
>     6 OT LS       0.19E-01    8.9                     6292.7883553971
>     7 OT CG       0.19E-01    9.5    10.25590581     11708.0244255459  2.44E+03
>     8 OT LS       0.94E-02    8.8                    11969.1303873198
>     9 OT CG       0.94E-02    9.5    13.22020338     17264.1530590901  5.56E+03
>    10 OT LS       0.47E-02    9.3                      440.1385496819
>    11 OT CG       0.47E-02   10.5    10.84986418      1809.1987721011 -1.55E+04
>    12 OT LS       0.24E-02    8.7                    -9010.1102604209
>    13 OT CG       0.24E-02    9.5    11.14977863     -8860.5442546787 -1.07E+04
>    14 OT LS       0.12E-02    8.7                   -17904.0400126385
>    15 OT CG       0.12E-02    9.6    13.08504532    -21173.4656772499 -1.23E+04
>    16 OT LS       0.61E-03    8.8                   -36955.6087684838
>    17 OT CG       0.61E-03    9.5    15.21462847    -86265.6674597911 -6.51E+04
>    18 OT LS       0.45E-03    8.8                  -201257.6097701387
>    19 OT CG       0.45E-03   10.0    21.70841463   -231606.6519578753 -1.45E+05
>    20 OT LS       0.18E-03    8.7                  -126318.8335739620
>  ----------------------------------- OT ---------------------------------------
>  ----------------------------------- OT ---------------------------------------
>     1 OT CG       0.15E+00   19.0    55.01598291   -303091.2201183116 -7.15E+04
>     2 OT LS       0.75E-01    8.8                   -13827.5476754934
>     3 OT CG       0.75E-01    9.4    29.19643290    -21191.3568458254  2.82E+05
>     4 OT LS       0.37E-01    9.3                     6164.3280063715
>     5 OT CG       0.37E-01    9.7    18.27946898      9663.1892847422  3.09E+04
>     6 OT LS       0.19E-01    8.7                    17637.0905403182
>     7 OT CG       0.19E-01    9.5    25.80109603       -41.8555446096 -9.71E+03
>     8 OT LS       0.94E-02    9.4                    15111.7311860815
>     9 OT CG       0.94E-02    9.6    17.80296834      5504.6103891014  5.55E+03
>    10 OT LS       0.47E-02    8.7                    -9120.3095962266
>    11 OT CG       0.47E-02   10.8    29.57256729    -17272.8718501564 -2.28E+04
>    12 OT LS       0.23E-02    8.9                      256.9190714106
>    13 OT CG       0.23E-02   10.1    23.61896943    -10444.4799316907  6.83E+03
>    14 OT LS       0.12E-02    8.8                    -2175.0933798563
>    15 OT CG       0.12E-02    9.5    33.28645147    -28306.3546421646 -1.79E+04
>    16 OT LS       0.58E-03    8.7                   -23361.9564416575
>    17 OT CG       0.58E-03    9.5    36.75975855    -45218.3529601046 -1.69E+04
>    18 OT LS       0.29E-03    8.7                   -21344.1126797873
>    19 OT CG       0.29E-03   11.1    40.63940778    -57044.7171713477 -1.18E+04
>    20 OT LS       0.15E-03   10.6                   -64095.2470229323
>  ----------------------------------- OT ---------------------------------------
>  ----------------------------------- OT ---------------------------------------
>     1 OT CG       0.15E+00   20.7    32.84827439    -43530.6779987434  1.35E+04
>     2 OT LS       0.75E-01    8.7                    -4247.1169918793
>     3 OT CG       0.75E-01    9.6    12.84651021     13454.1961742462  5.70E+04
>     4 OT LS       0.38E-01    8.7                     5878.8972648354
>     5 OT CG       0.38E-01    9.5    14.40359958     24491.3537461535  1.10E+04
>     6 OT LS       0.19E-01    8.8                    16982.3569638412
>     7 OT CG       0.19E-01    9.6    14.04116608     15809.4731631853 -8.68E+03
>     8 OT LS       0.94E-02    8.7                    13274.6176720042
>     9 OT CG       0.94E-02    9.5    10.55498077     16620.7477467228  8.11E+02
>    10 OT LS       0.47E-02    8.8                    21262.0329072758
>    11 OT CG       0.47E-02    9.5    11.24417203      7647.3114578911 -8.97E+03
>    12 OT LS       0.24E-02    8.7                    -4620.9801941348
>    13 OT CG       0.24E-02    9.6    11.17450752      5735.9160154671 -1.91E+03
>    14 OT LS       0.12E-02    8.8                    16595.3419511277
>    15 OT CG       0.12E-02    9.7    12.73350407      6615.4770773492  8.80E+02
>    16 OT LS       0.60E-03    9.5                    -4858.4905921913
>    17 OT CG       0.60E-03    9.5    17.06614684    -18505.1698092462 -2.51E+04
>    18 OT LS       0.30E-03    8.8                   -16510.5257354469
>    19 OT CG       0.30E-03    9.6    18.67317161    -29837.5115044920 -1.13E+04
>    20 OT LS       0.17E-03    9.2                   -50810.1240964150
>  ----------------------------------- OT ---------------------------------------
>  ----------------------------------- OT ---------------------------------------
>     1 OT CG       0.15E+00   20.0    34.18087037    -63880.3275551089 -3.40E+04
>     2 OT LS       0.75E-01    8.7                    11102.7951818560
>     3 OT CG       0.75E-01    9.5    16.97013324     13010.6911438830  7.69E+04
>     4 OT LS       0.37E-01    8.7                    10218.7000499332
>     5 OT CG       0.37E-01    9.4    19.11439483      6738.0975872246 -6.27E+03
>     6 OT LS       0.19E-01    8.7                     2152.9985606293
>     7 OT CG       0.19E-01    9.4    14.10386426     16124.4792234045  9.39E+03
>     8 OT LS       0.94E-02    8.7                    18622.9809378102
>     9 OT CG       0.94E-02    9.7    13.38733054      8907.9612812769 -7.22E+03
>    10 OT LS       0.47E-02    9.1                    -4385.7333658927
>    11 OT CG       0.47E-02    9.5    11.32659887      9083.0094899231  1.75E+02
>    12 OT LS       0.24E-02    8.8                     8983.6293872184
>    13 OT CG       0.24E-02   10.4    15.48570175     17690.7307290363  8.61E+03
>    14 OT LS       0.12E-02    8.6                     4424.0861120781
>    15 OT CG       0.12E-02    9.4    11.26570480       603.3675243938 -1.71E+04
>    16 OT LS       0.62E-03    8.8                   -17841.3731696137
>    17 OT CG       0.62E-03    9.4    20.46730835    -31698.4623769681 -3.23E+04
>    18 OT LS       0.30E-03    8.7                    -2859.9254300738
>    19 OT CG       0.30E-03    9.8    17.59724609    -26266.0262651212  5.43E+03
>    20 OT LS       0.16E-03    8.7                   -35171.6615426007
>  ----------------------------------- OT ---------------------------------------
>  ----------------------------------- OT ---------------------------------------
>     1 OT CG       0.15E+00   18.8    28.51774691    -19444.1649483434  6.82E+03
>     2 OT LS       0.75E-01    8.8                     9938.4525663009
>     3 OT CG       0.75E-01    9.6    15.56335740      8592.0250900205  2.80E+04
>     4 OT LS       0.37E-01    9.7                    27297.6406004072
>     5 OT CG       0.37E-01   12.3    13.00581731     14538.8489607548  5.95E+03
>     6 OT LS       0.19E-01    9.0                     9240.2545515611
>     7 OT CG       0.19E-01   10.0    10.04884641      7678.6463566507 -6.86E+03
>     8 OT LS       0.94E-02    9.0                    11768.1012889820
>     9 OT CG       0.94E-02   11.3    10.89504631     22910.2942034982  1.52E+04
>    10 OT LS       0.47E-02    8.8                    12342.8113540155
>    11 OT CG       0.47E-02   10.2    11.85566599      9817.1022867433 -1.31E+04
>    12 OT LS       0.23E-02    8.7                    10185.2530345840
>    13 OT CG       0.23E-02    9.6    12.00432884      9270.9870259300 -5.46E+02
>    14 OT LS       0.12E-02    8.8                     2126.1795722368
>    15 OT CG       0.12E-02    9.7    13.14795746     -2787.4974878007 -1.21E+04
>    16 OT LS       0.60E-03   10.6                    -6460.3154775535
>    17 OT CG       0.60E-03    9.6    14.74505818     -7132.9476831047 -4.35E+03
>    18 OT LS       0.30E-03    8.9                   -11225.7389275530
>    19 OT CG       0.30E-03    9.5    18.14553940    -38155.2733585050 -3.10E+04
> 
> --------------------------------------
> 
> Best,
> Xiaoming Wang  
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==============================
Thomas D. Kühne
Dynamics of Condensed Matter
Chair of Theoretical Chemistry
University of Paderborn
Warburger Str. 100
D-33098 Paderborn
Germany
tdku... at mail.upb.de
+49/(0)5251/60-5726

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