[CP2K-user] [CP2K:20571] Re: Au pseudopotential and basis set refinement for range separated functional

[Frederick Stein]

Dear Vladislav,
If the basis set is large enough, it does not matter for what functional it 
has been optimized. This does not apply to pseudopotentials. Those 
optimized for PBE0 may work in case of standard elements (HCNO) but not 
necessarily for transition metals. In case of an optimization, they should 
be a reasonable first guess. Try to optimize them and compare the results.
I have no experience in creating basis sets with the atom code. Please 
consult Jürg Hutter, he is the most experience here regarding basis set and 
pseudopotential optimizations (compare his extensive collection of 
self-optimized basis sets and pseudopotentials 
https://github.com/juerghutter/BASIS and 
https://github.com/juerghutter/GTH). I do have some experience with 
optimizing basis sets using a script provided by CP2K 
(https://github.com/cp2k/cp2k/tree/master/tools/scriptmini) to optimize 
correlation consistent basis sets.
Best,
Frederick

Vladislav Sláma schrieb am Donnerstag, 15. August 2024 um 10:50:43 UTC+2:

> Dear Frederick,
> Thank you very much for your suggestions regarding the pseudopotential. Indeed, 
> I copied the XC section from my testing calculations with the 
> pseudopotentials and basis optimized for the PBE0 without any big changes. 
> I'll try to look more into  ATOM%USE_GAUSS_HERMITE and ATOM%GRID_POINTS_GH 
> options to refine the pseudopotential even more. In general do you think 
> that the pseudopotentials and basis optimized for hybrid functionals (for 
> example PBE0) should be also good enough to be used with the range 
> separated hybrid functionals? I did some calculations of the excited states 
> of a small gold nanoparticle functionalized with one photoactive 
> biomolecule (with linker long enough tot to have charge transfer between 
> them) and I see quite large mixing between the gold and molecular 
> excitations. I wanted to be sure that the mixing is the real effect or just 
> an artifact originating from the improper pseudopotential and basis for the 
> range separated functional. This was my original motivation for the fitting.
> I would like to ask you one more question related to the basis set 
> fitting. Is the correct procedure to fit the GAUSSIAN orbitals and then do 
> the contraction to DZVP basis with some other code, or is it possible to do 
> it directly also in CP2K within the ATOM code and obtain coefficients and 
> exponents of the contracted basis?
>
> Thank you again for your insight. Best wishes,
> Vladislav
>
> Dne středa 14. srpna 2024 v 18:03:21 UTC+2 uživatel Frederick Stein napsal:
>
>> Dear Vladislav,
>> Generally, pseudopotentials optimized for hybrid functionals are a good 
>> first guess. I implemented pseudopotential optimization with the 
>> longrange-operator some years ago and optimized it for a few elements. 
>> IIRC, the relevant keywords are here:
>> - ATOM%USE_GAUSS_HERMITE (better convergence) and ATOM%GRID_POINTS_GH to 
>> tune the accuracy of the longrange operator
>> - ATOM%EXCHANGE_INTEGRALS requires the default NUMERIC (analytic 
>> integrals are not available for the longrange operator)
>> - HF%SCREENING and HF%MEMORY are ignored (the sections were just copied 
>> from the original HF section)
>> - check convergence of EPS_SCF and GRID_POINTS keywords and the ACCURACY 
>> keyword in the POWELL section
>> - The assignment of orbitals to occupied/semicore/core must be correct
>> Consult the regtests ATOM/regtest-pseudo/C-rsPBE-* for further reference 
>> (regtests are supposed to run fast).
>> HTH,
>> Frederick
>>
>> Vladislav Sláma schrieb am Mittwoch, 14. August 2024 um 14:37:11 UTC+2:
>>
>>> Hello,
>>>
>>> I would like to use wB97XD functional (or some other range-separated 
>>> one) with Au atoms for which I would like to fit pseudopotential and DZVP 
>>> basis set. With pseudopotential I tried to follow what I have found in the 
>>> test folder and started from the PBE pseudopotential parameters.
>>>
>>> 1) I would like to ask you if the input for the pseudopotential 
>>> parameters fitting with wB97XD is reasonable, because I’ve never done such 
>>> calculations?
>>>
>>> 2) What would be the correct strategy to get the DZVP basis set for the 
>>> Au atoms with fitted pseudopotential? The only calculation I managed to run 
>>> successfully (not sure if it is correct) was to fit the GAUSSIAN basis set. 
>>> However, for the CONTRACTED_GTO calculation always failed, sometimes 
>>> without specifying the error. Could you please suggest me how to do this 
>>> calculation? I’ve never needed to fit my own basis and pseudopotential so 
>>> any suggestion or advice is greatly appreciated.
>>>
>>> I’m including the input and output files in the attachment and below 
>>> also the input for the GAUSSIAN basis set generation.
>>>
>>> Best wishes and thank you for your help,
>>>
>>> Vladislav
>>>
>>>
>>> Input I used for GAUSSIAN basis set fitting:
>>>
>>>  &GLOBAL
>>>   PROGRAM_NAME ATOM
>>> &END GLOBAL
>>> &ATOM
>>>   ELEMENT Au
>>>   RUN_TYPE BASIS_OPTIMIZATION
>>>   ELECTRON_CONFIGURATION  CORE 5d10 6s1
>>>   CORE [Xe] 4f14
>>>   MAX_ANGULAR_MOMENTUM 3
>>>   COULOMB_INTEGRALS ANALYTIC
>>>   EXCHANGE_INTEGRALS NUMERIC
>>>   &METHOD
>>>      METHOD_TYPE  KOHN-SHAM
>>>      RELATIVISTIC DKH(3)
>>>      &XC
>>>         &XC_FUNCTIONAL
>>>            &HYB_GGA_XC_WB97X_D
>>>            &END  HYB_GGA_XC_WB97X_D
>>>         &END XC_FUNCTIONAL
>>>         &HF
>>>           FRACTION 1.000
>>>           &SCREENING
>>>             EPS_SCHWARZ 1.0E-14
>>>             SCREEN_ON_INITIAL_P TRUE
>>>           &END
>>>           &INTERACTION_POTENTIAL
>>>              POTENTIAL_TYPE MIX_CL
>>>              SCALE_COULOMB   0.22036
>>>              SCALE_LONGRANGE 0.77964
>>>              OMEGA 0.20
>>>           &END
>>>           &MEMORY
>>>             MAX_MEMORY 4000
>>>             EPS_STORAGE_SCALING 0.1
>>>           &END
>>>         &END
>>>      &END XC
>>>   &END METHOD
>>>   &OPTIMIZATION
>>>     MAX_ITER 500
>>>     EPS_SCF 1.e-08
>>>   &END
>>>   &PP_BASIS
>>>       NUM_GTO  6 6 6
>>>       S_EXPONENTS 3.73260507 1.83419039 0.80906390 0.34515101 0.13836655 
>>> 0.04967010
>>>       P_EXPONENTS 3.73260507 1.83419039 0.80906390 0.34515101 0.13836655 
>>> 0.04967010
>>>       D_EXPONENTS 3.73260507 1.83419039 0.80906390 0.34515101 0.13836655 
>>> 0.04967010
>>>      EPS_EIGENVALUE 1.E-14
>>>   &END PP_BASIS
>>>   &POTENTIAL
>>>     PSEUDO_TYPE GTH
>>>     &GTH_POTENTIAL
>>>     1    0   10    0
>>>     0.59017106458211       1   11.68962795194189
>>>        3
>>>     0.52046766556862       2    2.20132630023183   -1.04609353504732
>>>                                                     2.87007982647554
>>>     0.63876105996853       2    0.42941169563709   -0.86977143557004
>>>                                                     2.07606707053651
>>>     0.44087154543382       2   -4.71769832312536    0.72776406084227
>>>                                                    -1.72921082494821
>>>     &END
>>>   &END POTENTIAL
>>>   &POWELL
>>>      ACCURACY 1.e-8
>>>      STEP_SIZE 0.3
>>>   &END POWELL
>>> &END ATOM
>>>
>>

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