[CP2K-user] [CP2K:16799] CP2K to study ORR mechanism for MOFs

DMITRII Drugov dresearcher1991 at gmail.com
Fri Apr 1 14:09:43 UTC 2022


Dear Anton,

Thank you for your reply.
I set up LSD and multiplicity 2 only because I directly create a slab 011 
from cif of zif-8 by Avogadro software.
That gave me odd number of electrons. I also realised that 10-7 even 10-6 
will result in a strong drift for convergence. 
I will try 10-5 instead for correct slab structure.
I am a bit puzzled with slab termination as to create a facet of interest 
by direct translation of unit cell is a bit difficult. 
https://www.youtube.com/watch?v=ywR5pWqbllE
It is difficult to find a right center of symmetry without creating 
unbounded atoms. Chemistry of termination is also different depending how 
deep you slice it. I attached output file from run with previous settings 
in case you are interested, but that structure is unreasonable. I also got 
weird metal-like dos because of odd number of electrons and poor Avogadro 
slab preparation job.

Would you be able to look at facets which I created for non-periodic 
calculations and tell how reasonable to study ORR on them, or it is better 
to stick to periodic cif like structure to do ORR studies?

Do you think when I do reaction coordinate studies according to CHE method, 
should I consider only metal as an absorption site or nitrogen atom of 
imidazolium ligand as well? Ideally I would chose only one adsorption 
center. 

Best,
Dmitrii


On Friday, April 1, 2022 at 10:46:11 PM UTC+10 anton.s.l... at gmail.com wrote:

> Dear Dmitrii,
>
> how did you obtain the xyz? Did you just export it from CIF? It looks like 
> it is full of disordered hydrogen atoms.
>
> MULTIPLICITY 2 
>>
> Are you sure?
>
> What do you think I need to change for energy calculations, expect of 
>> deeper EPS_SCF from 1.0E-6 to 1.0E-7 or -8?
>>
> I don't know. AFAIR, the default is 1e-5, I used to lower it to 1e-6, 
> while 1.0e-7 resulted in very slow convergence (I mean that the calculation 
> reached the residues of ca 1e-6 and then started to turning around it, 
> until "accidentally" reached 1e-7 -- I guess that some other parameters are 
> to be tuned to avoid numeric noise). Anyway, you always could check the 
> consistency w.r.t. to the considered parameter by yourself. The key point 
> in your case is to get rid of numeric noise in gradients -- you can assess 
> it via observing the course of your geometry optimization (if you see some 
> random moves around the equilibrium rather than smooth convergence to it, 
> this might be the case).
>
> Do I need to use spin polarisation for Co and Zn atoms when I calculate 
>> adsorption energy for ORR reaction coordinate, or I can reach desirably 
>> accuracy without it? My job is to compare different facets reactivity for 
>> ORR.
>>
> I probably don't understand your question. If your system is paramagnetic, 
> you have to use the spin-unrestricted formalism (LSD aka UKS) anyway.
>
> I don't think the idea of crystallographic facets makes real sense in the 
> case of MOFs. The active centers in the case of MOFs are either the metal 
> ions with the coordinated atoms, or the fragments of ligands, these centers 
> are unlikely to be affected if you change the facet.
>
> Yours,
> Anton
>
> нд, 27 бер. 2022 р. о 08:47 DMITRII Drugov <dresear... at gmail.com> пише:
>
>> Dear Anton,
>>
>> Thank you for your reply.
>> I even did not think about low symmetry of MOFs. Thank you for this point.
>> I attach my input file below for cell_opt first, then I will do energy 
>> calculation.
>> Could you please have a look at my settings and express your opinion on 
>> its accuracy?
>> What do you think I need to change for energy calculations, expect of 
>> deeper EPS_SCF from 1.0E-6 to 1.0E-7 or -8?
>> Do I need to use spin polarisation for Co and Zn atoms when I calculate 
>> adsorption energy for ORR reaction coordinate, or I can reach desirably 
>> accuracy without it? My job is to compare different facets reactivity for 
>> ORR.
>>
>> Best,
>> Dmitrii
>>
>> &GLOBAL
>>   PROJECT MOF_011_optimisation_larger_cell 
>>   RUN_TYPE CELL_OPT
>>   PRINT_LEVEL MEDIUM
>>   !EXTENDED_FFT_LENGTHS
>> &END GLOBAL
>> &FORCE_EVAL
>> STRESS_TENSOR ANALYTICAL
>>   METHOD QS
>>   &DFT
>>     BASIS_SET_FILE_NAME BASIS_MOLOPT
>>     POTENTIAL_FILE_NAME GTH_POTENTIALS
>>     LSD
>>     CHARGE 0
>>     MULTIPLICITY 2
>>     &MGRID
>>       CUTOFF 800
>>       NGRIDS 5
>>       REL_CUTOFF 70
>>     &END MGRID
>>     &QS
>>       EPS_DEFAULT 1.0E-14
>>       !WF_INTERPOLATION ASPC
>>     &END QS
>>    &SCF
>>       SCF_GUESS ATOMIC
>>       EPS_SCF 1.0E-6
>>       MAX_SCF 300
>>       &OT
>>        MINIMIZER CG
>>        PRECONDITIONER FULL_KINETIC
>>        # ENERGY_GAP 0.01
>>        &END OT
>>       &OUTER_SCF
>>        EPS_SCF 1E-6
>>        MAX_SCF 300
>>       &END 
>>       !CHOLESKY INVERSE
>>       !ADDED_MOS 100
>>       !&SMEAR ON
>>        ! METHOD FERMI_DIRAC
>>        ! ELECTRONIC_TEMPERATURE [K] 1000
>>      ! &END SMEAR
>>       !&DIAGONALIZATION
>>        ! ALGORITHM STANDARD
>>       !&END DIAGONALIZATION
>>       !&MIXING
>>        ! METHOD BROYDEN_MIXING
>>         !ALPHA 0.4                
>>         !NBROYDEN 8
>>       !&END MIXING
>>     &END SCF
>>     &XC
>>       &XC_FUNCTIONAL
>>         &PBE
>>         &END PBE
>>       &END XC_FUNCTIONAL
>>       &vdW_POTENTIAL
>>             DISPERSION_FUNCTIONAL PAIR_POTENTIAL
>>              &PAIR_POTENTIAL
>>                 PARAMETER_FILE_NAME dftd3.dat
>>                        TYPE DFTD3
>>                        REFERENCE_FUNCTIONAL PBE
>>                        R_CUTOFF 8.0
>>             &END PAIR_POTENTIAL
>>      &END vdW_POTENTIAL
>>     &END XC
>>     SURFACE_DIPOLE_CORRECTION T
>>     SURF_DIP_DIR Z
>>     &POISSON
>>       PERIODIC xy
>>       POISSON_SOLVER ANALYTIC
>>     &END POISSON
>>   &END DFT
>>   &SUBSYS
>>     &CELL
>>       ABC 18.55406 16.35222 50
>>       ALPHA_BETA_GAMMA 90.0 90.0 90.0
>>       PERIODIC xy
>>       SYMMETRY ORTHORHOMBIC
>>     &END CELL
>>     &COORD
>> C         2.69109      3.50908       2.31039
>> C         2.69109      12.34314      2.31039
>> C         0.51227      7.92611       3.89871
>> N         5.94837      3.44592       0.26929
>> N         1.20316      9.05092       3.62466
>> N         1.20316      6.8013        3.62466
>> N         5.94837      12.4063       0.26929
>> C         6.87686      10.39498      0
>> C         5.92646      4.78521       0.67203
>> C         2.43496      8.59814       3.1409
>> C         2.43496      7.25408       3.1409
>> C         6.87686      5.45724       0
>> C         5.92646      11.06701      0.67203
>> H         7.0639       9.48822       0.08937
>> H         5.34848      5.15102       1.30235
>> H         3.13933      9.1391        2.86446
>> H         3.13933      6.71312       2.86446
>> H         7.0639       6.364         0.08937
>> H         5.34848      10.7012       1.30235
>> C         2.26139      4.168         1.04379
>> C         2.26139      11.68422      1.04379
>> H         1.56208      4.79832       1.23086
>> H         2.83938      11.95708      0.32767
>> H         1.56208      11.0539       1.23086
>> H         2.83938      3.89514       0.32767
>> H         3.00789      4.62555       0.65058
>> H         2.30689      10.73099      1.14626
>> H         3.00789      11.22667      0.65058
>> H         2.30689      5.12123       1.14626
>> H         1.93449      3.50312       0.43134
>> H         1.35819      11.94159      0.83884
>> H         1.93449      12.3491       0.43134
>> H         1.35819      3.91063       0.83884
>> O         5.79166      7.92611       2.27822
>> Zn        4.81431      13.8838       0.89604
>> Zn        0.60158      10.90496      3.87488
>> C         6.93752      15.29816      2.4367
>> C         0.69089      10.88113      6.85373
>> N         3.68024      13.25705      2.37354
>> N         2.08951      12.13224      3.49836
>> N         0            11.15518      5.72892
>> N         5.94837      15.36131      1.52279
>> C         3.70215      13.65979      3.71283
>> C         2.75175      12.98777      4.38486
>> H         4.28013      14.29012      4.07864
>> H         6.48928      15.85222      5.64074
>> H         2.56471      13.07713      5.29162
>> C         7.36722      14.03155      3.09562
>> C         2.05244      10.27344      6.85373
>> H         2.83938      15.81052      1.4644
>> H         8.06653      14.21863      3.72594
>> H         2.36587      10.18765      5.95054
>> H         6.78923      13.31544      2.82276
>> H         6.62072      13.63835      3.55317
>> H         2.65402      10.83346      6.35805
>> H         7.32172      14.13403      4.04885
>> H         1.35819      15.82601      0.95323
>> H         1.93449      15.4185       1.36074
>> H         7.69412      13.4191       2.43074
>> H         2.01537      9.40362       6.44622
>> H         8.27042      13.82661      2.83825
>> O         3.83695      15.26599      6.85373
>> O         5.92646      12.31097      6.85373
>> Co        0.60158      4.94726       3.87488
>> Zn        4.81431      1.96842       0.89604
>> C         6.93752      0.55406       2.4367
>> C         0.69089      4.97109       6.85373
>> N         2.08951      3.71998       3.49836
>> N         3.68024      2.59517       2.37354
>> N         5.94837      0.49091       1.52279
>> N         0            4.69704       5.72892
>> C         2.75175      2.86445       4.38486
>> C         3.70215      2.19243       3.71283
>> H         2.56471      2.77509       5.29162
>> H         6.48928      0             5.64074
>> H         4.28013      1.5621        4.07864
>> C         7.36722      1.82067       3.09562
>> C         2.05244      5.57878       6.85373
>> H         2.83938      0.0417        1.4644
>> H         6.78923      2.53678       2.82276
>> H         2.36587      5.66457       5.95054
>> H         8.06653      1.63359       3.72594
>> H         7.32172      1.71819       4.04885
>> H         2.65402      5.01876       6.35805
>> H         6.62072      2.21387       3.55317
>> H         1.93449      0.43372       1.36074
>> H         1.35819      0.02621       0.95323
>> H         8.27042      2.02561       2.83825
>> H         2.01537      6.4486        6.44622
>> H         7.69412      2.43312       2.43074
>> O         3.83695      0.58623       6.85373
>> O         5.92646      3.54125       6.85373
>> C         17.36317     7.92611       3.89871
>> N         15.96455     4.57074       2.6476
>> N         14.37382     12.4063       1.52279
>> N         15.96455     11.28148      2.6476
>> N         14.37382     3.44592       1.52279
>> N         18.05406     9.05092       3.62466
>> N         18.05406     6.8013        3.62466
>> C         15.30231     5.45724       1.79207
>> C         14.35191     11.06701      1.12005
>> C         15.30231     10.39498      1.79207
>> C         14.35191     4.78521       1.12005
>> H         15.48935     6.364         1.70271
>> H         13.77393     10.7012       0.48972
>> H         15.48935     9.48822       1.70271
>> H         13.77393     5.15102       0.48972
>> C         10.68684     11.68422      0.74829
>> C         10.68684     4.168         0.74829
>> C         16.00162     7.92611       4.5064
>> H         9.98753      11.0539       0.56121
>> H         11.26483     3.89514       1.4644
>> H         15.68819     8.8293        4.59219
>> H         15.68819     7.02292       4.59219
>> H         9.98753      4.79832       0.56121
>> H         11.26483     11.95708      1.4644
>> H         11.43334     11.22667      1.14149
>> H         10.73234     5.12123       0.64581
>> H         15.40004     7.43043       3.94638
>> H         15.40004     8.42179       3.94638
>> H         11.43334     4.62555       1.14149
>> H         10.73234     10.73099      0.64581
>> H         10.35994     12.3491       1.36074
>> H         9.78364      3.91063       0.95323
>> H         16.03869     7.5186        5.37622
>> H         16.03869     8.33362       5.37622
>> H         10.35994     3.50312       1.36074
>> H         9.78364      11.94159      0.95323
>> O         12.1276      7.92611       2.46887
>> Zn        13.23976     13.8838       0.89604
>> Zn        17.45248     10.90496      3.87488
>> C         15.36297     12.46945      2.4367
>> C         11.11654     15.42446      2.31039
>> C         17.54179     10.88113      6.85373
>> N         14.37382     15.36131      0.26929
>> N         10.51496     15.63536      3.49836
>> N         16.8509      11.15518      5.72892
>> N         12.10569     14.51055      2.37354
>> C         11.1772      14.77984      4.38486
>> C         15.6191      11.63894      6.1817
>> C         12.1276      14.10781      3.71283
>> H         10.99016     14.69047      5.29162
>> H         14.91473     11.91538      5.64074
>> H         12.70558     13.47749      4.07864
>> C         15.79267     13.73605      3.09562
>> H         15.21468     14.45217      2.82276
>> H         16.49198     13.54898      3.72594
>> H         11.26483     15.81052      0.32767
>> H         15.74717     13.63358      4.04885
>> H         15.04617     14.12926      3.55317
>> H         16.69587     13.941        2.83825
>> H         16.11957     14.3485       2.43074
>> H         10.35994     15.4185       0.43134
>> H         9.78364      15.82601      0.83884
>> O         12.2624      12.50162      6.85373
>> O         14.35191     15.45663      6.85373
>> Zn        17.45248     4.94726       3.87488
>> Zn        13.23976     1.96842       0.89604
>> C         15.36297     3.38277       2.4367
>> C         11.11654     0.42776       2.31039
>> C         17.54179     4.97109       6.85373
>> N         14.37382     0.49091       0.26929
>> N         12.10569     1.34167       2.37354
>> N         16.8509      4.69704       5.72892
>> N         10.51496     0.21686       3.49836
>> C         12.1276      1.74441       3.71283
>> C         15.6191      4.21328       6.1817
>> C         11.1772      1.07238       4.38486
>> H         12.70558     2.37473       4.07864
>> H         14.91473     3.93684       5.64074
>> H         10.99016     1.16175       5.29162
>> C         15.79267     2.11617       3.09562
>> H         16.49198     2.30324       3.72594
>> H         15.21468     1.40005       2.82276
>> H         11.26483     0.0417        0.32767
>> H         15.04617     1.72296       3.55317
>> H         15.74717     2.21864       4.04885
>> H         16.11957     1.50372       2.43074
>> H         16.69587     1.91122       2.83825
>> H         9.78364      0.02621       0.83884
>> H         10.35994     0.43372       0.43134
>> O         12.2624      3.3506        6.85373
>> O         14.35191     0.39559       6.85373
>>    &END COORD
>>     &KIND Co 
>>       BASIS_SET DZVP-MOLOPT-SR-GTH 
>>       POTENTIAL GTH-PBE-q17
>>     &END KIND
>>     &KIND Zn 
>>       BASIS_SET DZVP-MOLOPT-SR-GTH
>>       POTENTIAL GTH-PBE-q12
>>     &END KIND
>>     &KIND O
>>       BASIS_SET TZVP-MOLOPT-GTH
>>       POTENTIAL GTH-PBE-q6
>>     &END KIND
>>     &KIND C
>>       BASIS_SET TZVP-MOLOPT-GTH
>>       POTENTIAL GTH-PBE-q4
>>     &END KIND
>>     &KIND H                              
>>       BASIS_SET TZVP-MOLOPT-GTH
>>       POTENTIAL GTH-PBE-q1
>>     &END KIND
>>     &KIND N
>>       BASIS_SET TZVP-MOLOPT-GTH
>>       POTENTIAL GTH-PBE-q5
>>     &END KIND
>>    &END SUBSYS
>> &END FORCE_EVAL
>> &MOTION
>>   &GEO_OPT
>>    OPTIMIZER LBFGS
>>    MAX_ITER 300
>>   &END GEO_OPT
>>   &CELL_OPT
>>     EXTERNAL_PRESSURE [bar] 0.0
>>     KEEP_ANGLES TRUE
>>     KEEP_SYMMETRY TRUE
>>     OPTIMIZER LBFGS
>>   &END
>>  &END MOTION
>> &END
>>   
>>
>>  
>>
>> On Friday, March 25, 2022 at 8:32:42 PM UTC+10 anton.s.l... at gmail.com 
>> wrote:
>>
>>> Dear Dmitrii,
>>>
>>> CP2k has implementation of k-points, but it could be incompatible with 
>>> some methods and features.
>>>
>>> But why do you need it? MOFs cells are typically large and have low 
>>> symmetry.
>>>
>>> Yours,
>>> Anton
>>>
>>> пт, 25 бер. 2022 р. о 10:38 DMITRII Drugov <dresear... at gmail.com> пише:
>>>
>>>> Dear CP2K users, 
>>>>
>>>> Could you please share your thoughts on correct CP2K settings to study 
>>>> oxygen reaction reaction on MOFs surface (186 atoms, C, H, O, N, Zn)? I 
>>>> used to conduct similar job on Quantum Espresso for to study HER on 
>>>> graphite slab (86 atoms) and it took ages to finish single energy 
>>>> calculation with soft potentials (ecutrho =   0.4000000000d+03
>>>>   ecutwfc =   0.5000000000d+02). According to my experience at gamma 
>>>> point CP2K is much faster but I never added k-point mesh to CP2K.
>>>> Could you please let me know what my CP2K should be? Does CP2K allow to 
>>>> set up k-points for energy calculation? My system is a slab with vacuum of 
>>>> 2*x or y in z dimension.
>>>>
>>>> Best regards,
>>>> Dmitrii
>>>>
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>>>>
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