[CP2K-user] [CP2K:21140] Re: Electronic Convergence Issue in Geometry Optimization of Molecule Adsorption

Rishikanta Mayengbam rishikantamayengbam at gmail.com
Thu Feb 13 06:14:06 UTC 2025


Thanks Tyler.

 My system is a perovskite slab over which an organic molecule is placed, 
both are semiconductors.  

Now, I use diagonalization and removed smearing.  The main issue was with 
the POISSON_PSOLVER, which was set to MT.  With ANALYTIC, it converges 
quite smoothly and fast (in 4 hours, 128 cores).  
The optimized structure quite resembles the one obtained from VASP package.

I would like to know: Is dipole corrections very essential for subsequent 
MD simulations for the optimized structure? 


On Wednesday, February 12, 2025 at 12:53:30 AM UTC+8 Tyler Sterling wrote:

> It seems like your structure is metallic since you are using smearing and 
> added mos. In which case, you shouldn't be using OT or other minimization 
> methods. Only use diagonalization. Also, if the structure is blowing up, 
> make sure it is charge neutral. 
>
> On Tuesday, February 11, 2025 at 12:19:25 AM UTC-7 Rishikanta Mayengbam 
> wrote:
>
>> Hi users,
>>
>> After the geometry optimization with OT method, the surface layers of the 
>> perovskite slab become so weird, some atoms of the molecule break and move 
>> far upwards. 
>>
>> So, I tried with the standard diagonalization. But after several steps, I 
>> stopped the geometry optimization in the mid-way because the structure 
>> changed in the similar fashion as above. 
>> I have no idea what is going wrong here.
>>
>> Can someone suggest something? 
>>
>>
>> On Thursday, February 6, 2025 at 4:34:05 PM UTC+8 Rishikanta Mayengbam 
>> wrote:
>>
>>> Dear Prof. Marcella,
>>>
>>> Thank you for your suggestion! I tried applying smearing to the 
>>> occupation numbers and reducing the alpha parameter in the density mixing, 
>>> and it worked wonderfully. The convergence has improved significantly, and 
>>> the calculations are now much more stable.
>>> The OT method resulted in a weird optimized structure. 
>>>
>>>
>>>
>>> On Sat, Feb 1, 2025 at 2:41 PM Rishikanta Mayengbam <
>>> rishikant... at gmail.com> wrote:
>>>
>>>> Thanks for the response. 
>>>>
>>>> It was not able to converge even within 4000 steps. So, I tried many 
>>>> things, loosening the convergence criteria, changing cut-off and relative 
>>>> cut offs, etc. I haven't tried with the smearing, but have tried reducing 
>>>> the mixing alpha parameter. 
>>>> Finally, I used CG Minimiser as follows and it's converging. Is this 
>>>> approach correct?
>>>>
>>>> &GLOBAL
>>>>    PRINT_LEVEL  MEDIUM
>>>>    PROJECT_NAME CsPb_Br3_TmPyPB_OPT
>>>>    RUN_TYPE  GEO_OPT
>>>>    EXTENDED_FFT_LENGTHS T
>>>> &END GLOBAL
>>>>
>>>> &FORCE_EVAL
>>>>   METHOD  QS
>>>>   &DFT
>>>>     UKS .FALSE. 
>>>>     BASIS_SET_FILE_NAME BASIS_MOLOPT
>>>>     POTENTIAL_FILE_NAME POTENTIAL 
>>>>     &MGRID
>>>>       NGRIDS 4
>>>>       CUTOFF 500
>>>>       REL_CUTOFF 50
>>>>     &END MGRID
>>>>     &QS
>>>>       METHOD GPW
>>>>       EPS_DEFAULT 1.000E-12
>>>>     &END QS
>>>>     &POISSON
>>>>       PERIODIC XZ
>>>>       PSOLVER MT
>>>>     &END POISSON
>>>>     &SCF
>>>>       EPS_SCF 1.0E-6
>>>>       SCF_GUESS RESTART
>>>>       MAX_SCF 5000
>>>>         &OT
>>>>         MINIMIZER CG
>>>>         PRECONDITIONER FULL_SINGLE_INVERSE
>>>>         &END OT
>>>>       &OUTER_SCF          
>>>>         MAX_SCF 500
>>>>         EPS_SCF 1.0E-5
>>>>       &END OUTER_SCF
>>>>     &END SCF
>>>>     &XC
>>>>       &XC_FUNCTIONAL
>>>>          &PBE
>>>>          &END PBE
>>>>       &END XC_FUNCTIONAL
>>>>       &VDW_POTENTIAL
>>>>          POTENTIAL_TYPE PAIR_POTENTIAL 
>>>>          &PAIR_POTENTIAL
>>>>             PARAMETER_FILE_NAME dftd3.dat
>>>>             TYPE DFTD3
>>>>             REFERENCE_FUNCTIONAL PBE
>>>>             R_CUTOFF [angstrom] 16
>>>>          &END
>>>>       &END VDW_POTENTIAL
>>>>     &END XC
>>>>     &PRINT
>>>>       &MULLIKEN OFF
>>>>       &END
>>>>       &HIRSHFELD OFF
>>>>       &END
>>>>     &END PRINT
>>>>   &END DFT
>>>>   &SUBSYS
>>>>     &CELL
>>>>       A   24.8975601196000014    0.0000000000000000   
>>>>  0.0000000000000000
>>>>       B   0.0000000000000000    55.6124382018999981   
>>>>  0.0000000000000000
>>>>       C   0.0000000000000000     0.0000000000000000   
>>>> 24.9615383147999985
>>>>       PERIODIC  XZ
>>>>     &END CELL
>>>>     &TOPOLOGY
>>>>       COORD_FILE_NAME CsBr-TmPyPB.xyz
>>>>       COORD_FILE_FORMAT XYZ
>>>>     &END
>>>>     &KIND  Cs
>>>>       BASIS_SET DZVP-MOLOPT-SR-GTH 
>>>>       POTENTIAL GTH-PBE-q9 
>>>>     &END KIND
>>>>     &KIND Pb
>>>>       BASIS_SET DZVP-MOLOPT-SR-GTH 
>>>>       POTENTIAL GTH-PBE-q4
>>>>     &END KIND
>>>>     &KIND Br 
>>>>       BASIS_SET  DZVP-MOLOPT-SR-GTH 
>>>>       POTENTIAL  GTH-PBE-q7
>>>>     &END KIND
>>>>     &KIND C
>>>>       BASIS_SET DZVP-MOLOPT-GTH
>>>>       POTENTIAL GTH-PBE-q4
>>>>     &END KIND
>>>>     &KIND N
>>>>      BASIS_SET DZVP-MOLOPT-GTH
>>>>      POTENTIAL GTH-PBE-q5
>>>>     &END KIND
>>>>     &KIND H
>>>>      BASIS_SET DZVP-MOLOPT-GTH
>>>>      POTENTIAL GTH-PBE-q1
>>>>     &END KIND
>>>>   &END SUBSYS
>>>> &END FORCE_EVAL
>>>>
>>>> &MOTION
>>>>  &GEO_OPT
>>>>    OPTIMIZER LBFGS
>>>>    MAX_ITER 1000
>>>>    MAX_DR [bohr] 0.002
>>>>    MAX_FORCE [hartree*bohr^-1] 3.000E-4
>>>>    RMS_DR [bohr] 0.002
>>>>    RMS_FORCE [hartree*bohr^-1] 3.000E-4
>>>>  &END GEO_OPT
>>>>
>>>>  &CONSTRAINT
>>>>    &FIXED_ATOMS
>>>>      LIST 1 2 3 4 5 6 ...........
>>>>    &END FIXED_ATOMS
>>>>  &END CONSTRAINT
>>>>
>>>>  &PRINT
>>>>    &TRAJECTORY
>>>>      &EACH
>>>>        GEO_OPT 5
>>>>      &END EACH
>>>>      FORMAT XYZ
>>>>    &END TRAJECTORY
>>>>    &VELOCITIES OFF  
>>>>    &END VELOCITIES
>>>>    &FORCES ON       
>>>>    &END FORCES
>>>>    &RESTART
>>>>      BACKUP_COPIES 1
>>>>      &EACH
>>>>        GEO_OPT 10
>>>>      &END EACH
>>>>    &END RESTART
>>>>  &END PRINT
>>>> &END MOTION
>>>>
>>>> On Friday, January 31, 2025 at 8:31:44 PM UTC+8 Marcella Iannuzzi wrote:
>>>>
>>>>> Hi ...
>>>>>
>>>>> How bad is the convergence? You might need smearing of the occupation 
>>>>> number and a smaller alpha parameter in the density mixing. 
>>>>> Regards
>>>>> marcella 
>>>>>
>>>>> On Thursday, January 30, 2025 at 5:24:09 PM UTC+1 
>>>>> rishikant... at gmail.com wrote:
>>>>>
>>>>>> *Dear CP2K Users,*
>>>>>>
>>>>>> I am running a *geometry optimization for a molecule adsorption 
>>>>>> system with vacuum along the y-axis*, but I am struggling to achieve *electronic 
>>>>>> SCF convergence even after 1000 iterations*. I would appreciate any 
>>>>>> suggestions on improving the convergence.
>>>>>>
>>>>>> Below is my input script:
>>>>>> &GLOBAL
>>>>>>    PRINT_LEVEL  MEDIUM
>>>>>>    PROJECT_NAME mol_absorp_OPT
>>>>>>    RUN_TYPE  GEO_OPT
>>>>>>    EXTENDED_FFT_LENGTHS T
>>>>>> &END GLOBAL
>>>>>>
>>>>>> &FORCE_EVAL
>>>>>>   METHOD  QS
>>>>>>   &DFT
>>>>>>     UKS .FALSE. 
>>>>>>     BASIS_SET_FILE_NAME BASIS_MOLOPT
>>>>>>     POTENTIAL_FILE_NAME POTENTIAL 
>>>>>>     &MGRID
>>>>>>       NGRIDS 4
>>>>>>       CUTOFF 600
>>>>>>       REL_CUTOFF 60
>>>>>>     &END MGRID
>>>>>>     &QS
>>>>>>       METHOD GPW
>>>>>>       EPS_DEFAULT 1.000E-12
>>>>>>     &END QS
>>>>>>     &POISSON
>>>>>>       PERIODIC XZ
>>>>>>       PSOLVER MT
>>>>>>     &END POISSON
>>>>>>     &SCF
>>>>>>       &DIAGONALIZATION ON
>>>>>>       &END DIAGONALIZATION
>>>>>>       &MIXING
>>>>>>         ALPHA 0.5
>>>>>>         METHOD PULAY_MIXING
>>>>>>         NBROYDEN 8
>>>>>>       &END MIXING
>>>>>>       EPS_SCF 1.0E-5
>>>>>>       SCF_GUESS ATOMIC
>>>>>>       MAX_SCF  5000
>>>>>>       ADDED_MOS 100
>>>>>>     &END SCF
>>>>>>     &XC
>>>>>>       &XC_FUNCTIONAL
>>>>>>          &PBE
>>>>>>          &END PBE
>>>>>>       &END XC_FUNCTIONAL
>>>>>>       &VDW_POTENTIAL
>>>>>>          POTENTIAL_TYPE PAIR_POTENTIAL 
>>>>>>          &PAIR_POTENTIAL
>>>>>>             PARAMETER_FILE_NAME dftd3.dat
>>>>>>             TYPE DFTD3
>>>>>>             REFERENCE_FUNCTIONAL PBE
>>>>>>             R_CUTOFF [angstrom] 16
>>>>>>          &END
>>>>>>       &END VDW_POTENTIAL
>>>>>>     &END XC
>>>>>>     &PRINT
>>>>>>       &MULLIKEN OFF
>>>>>>       &END
>>>>>>       &HIRSHFELD OFF
>>>>>>       &END
>>>>>>     &END PRINT
>>>>>>   &END DFT
>>>>>>   &SUBSYS
>>>>>>     &CELL
>>>>>>       A   24.8975601196000014    0.0000000000000000   
>>>>>>  0.0000000000000000
>>>>>>       B   0.0000000000000000    55.6124382018999981   
>>>>>>  0.0000000000000000
>>>>>>       C   0.0000000000000000     0.0000000000000000   
>>>>>> 24.9615383147999985
>>>>>>       PERIODIC  XZ
>>>>>>     &END CELL
>>>>>>     &TOPOLOGY
>>>>>>       COORD_FILE_NAME ABC.xyz
>>>>>>       COORD_FILE_FORMAT XYZ
>>>>>>     &END
>>>>>>     &KIND  Cs
>>>>>>       BASIS_SET DZVP-MOLOPT-SR-GTH 
>>>>>>       POTENTIAL GTH-PBE-q9 
>>>>>>     &END KIND
>>>>>>     &KIND Pb
>>>>>>       BASIS_SET DZVP-MOLOPT-SR-GTH 
>>>>>>       POTENTIAL GTH-PBE-q4
>>>>>>     &END KIND
>>>>>>     &KIND Br 
>>>>>>       BASIS_SET  DZVP-MOLOPT-SR-GTH 
>>>>>>       POTENTIAL  GTH-PBE-q7
>>>>>>     &END KIND
>>>>>>     &KIND C
>>>>>>       BASIS_SET DZVP-MOLOPT-GTH
>>>>>>       POTENTIAL GTH-PBE-q4
>>>>>>     &END KIND
>>>>>>     &KIND N
>>>>>>      BASIS_SET DZVP-MOLOPT-GTH
>>>>>>      POTENTIAL GTH-PBE-q5
>>>>>>     &END KIND
>>>>>>     &KIND H
>>>>>>      BASIS_SET DZVP-MOLOPT-GTH
>>>>>>      POTENTIAL GTH-PBE-q1
>>>>>>     &END KIND
>>>>>>   &END SUBSYS
>>>>>> &END FORCE_EVAL
>>>>>>
>>>>>> &MOTION
>>>>>>  &GEO_OPT
>>>>>>    OPTIMIZER BFGS
>>>>>>    MAX_ITER 500
>>>>>>    MAX_DR [bohr] 0.01
>>>>>>    MAX_FORCE [hartree*bohr^-1] 0.01
>>>>>>    RMS_DR [bohr] 0.01
>>>>>>    RMS_FORCE [hartree*bohr^-1] 0.01
>>>>>>  &END GEO_OPT
>>>>>>
>>>>>>  &CONSTRAINT
>>>>>>    &FIXED_ATOMS
>>>>>>      LIST 1 2 3 4 5 6 10 11 12 13 14 15 .........................
>>>>>>    &END FIXED_ATOMS
>>>>>>  &END CONSTRAINT
>>>>>>
>>>>>>  &PRINT
>>>>>>    &TRAJECTORY
>>>>>>      &EACH
>>>>>>        GEO_OPT 5
>>>>>>      &END EACH
>>>>>>      FORMAT XYZ
>>>>>>    &END TRAJECTORY
>>>>>>    &VELOCITIES OFF  
>>>>>>    &END VELOCITIES
>>>>>>    &FORCES ON      
>>>>>>    &END FORCES
>>>>>>    &RESTART
>>>>>>      BACKUP_COPIES 1
>>>>>>      &EACH
>>>>>>        GEO_OPT 10
>>>>>>      &END EACH
>>>>>>    &END RESTART
>>>>>>  &END PRINT
>>>>>> &END MOTION
>>>>>
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