[CP2K-user] [CP2K:20808] All-electron Geometry Optimization of EMIBF4

Jürg Hutter hutter at chem.uzh.ch
Thu Oct 24 07:53:52 UTC 2024


Hi
you should do the following steps to get this running:

1) Use OT optimizer
      &SCF
        MAX_SCF 50
        SCF_GUESS RESTART
        EPS_SCF 1E-6
        &OT
           PRECONDITIONER FULL_ALL
           MINIMIZER DIIS
        &END OT
      &END SCF
2) Use EPS_Defualt 1.E-10
3) Optimize the structure (at least SCF, maybe geometry) first with a GGA functional (e.g. PBE)
4) Restart from that orbitals and use SCREEN_ON_INITIAL_P TRUE
5) Increase MAX_MEMORY (if possible) so that all integrals are kept incore
6) USE ADMM
      &AUXILIARY_DENSITY_MATRIX_METHOD
        ADMM_TYPE ADMMQ
        EXCH_CORRECTION_FUNC PBEX
      &END AUXILIARY_DENSITY_MATRIX_METHOD
   with (add it)
      BASIS_SET_FILE_NAME BASIS_ADMM_ae
   and
      BASIS_SET AUX_FIT admm-2
7) Use BFGS for geometry optimizer, maybe even restart the Hessian from a previous GGA optimization
8) if the geometry optimization is not converging you might have to tighten the thresholds
     EPS_DEFAULT, EPS_SCF, EPS_SCHWARZ

With these changes, you need about 40 Gb of memory and on 36 core a geometry step takes 1-2 minutes.

regards
JH


________________________________________
From: cp2k at googlegroups.com <cp2k at googlegroups.com> on behalf of Nicholas Laws <nicholaslaws8 at gmail.com>
Sent: Wednesday, October 23, 2024 5:30 PM
To: cp2k
Subject: Re: [CP2K:20806] All-electron Geometry Optimization of EMIBF4

Thank you for the advice, Professor Hutter. I have since referenced the all-electron examples in the tests/QS sections and adjusted my input script accordingly (as seen in the attached .inp file). I have decided to separate the geometry optimizations into two separate simulations (one for EMIBF4 and one for EMI+). The content of this post refers to the geometry optimization of EMIBF4. However, after testing several SCF and GEO_OPT configurations, it seems that there are energy instabilities that occur after 5 energy evaluations as depicted here:

SCF WAVEFUNCTION OPTIMIZATION

  Step     Update method      Time    Convergence         Total energy    Change
  ------------------------------------------------------------------------------

  HFX_MEM_INFO| Est. max. program size before HFX [MiB]:                   91626
  HFX_MEM_INFO| Number of cart. primitive ERI's calculated:         150682718957
  HFX_MEM_INFO| Number of sph. ERI's calculated:                     54286634411
  HFX_MEM_INFO| Number of sph. ERI's stored in-core:                 29731009090
  HFX_MEM_INFO| Number of sph. ERI's stored on disk:                           0
  HFX_MEM_INFO| Number of sph. ERI's calculated on the fly:          24555625321
  HFX_MEM_INFO| Total memory consumption ERI's RAM [MiB]:                  64051
  HFX_MEM_INFO| Whereof max-vals [MiB]:                                      193
  HFX_MEM_INFO| Total compression factor ERI's RAM:                         3.54
  HFX_MEM_INFO| Total memory consumption ERI's disk [MiB]:                     0
  HFX_MEM_INFO| Total compression factor ERI's disk:                        0.00
  HFX_MEM_INFO| Size of density/Fock matrix [MiB]:                             4
  HFX_MEM_INFO| Size of buffers [MiB]:                                         5
  HFX_MEM_INFO| Est. max. program size after HFX  [MiB]:                   91793

     1 Pulay/Diag. 0.20E+00  105.6    93.15134943      -786.8938839625 -7.87E+02
     2 Pulay/Diag. 0.20E+00   59.5  1424.78843686      -787.9112236525 -1.02E+00
     3 Pulay/Diag. 0.20E+00   59.6     4.0852E+05      -804.4927698695 -1.66E+01
     4 Pulay/Diag. 0.20E+00   58.8     2.6603E+05     -1012.0913997227 -2.08E+02
     5 Pulay/Diag. 0.20E+00   60.1     1.2150E+05     -3042.9246578949 -2.03E+03
     6 Pulay/Diag. 0.20E+00   58.7     1.3437E+05     -4156.9505747502 -1.11E+03
     7 Pulay/Diag. 0.20E+00   59.4 58430.75278087     -4430.8543850289 -2.74E+02
     8 Pulay/Diag. 0.20E+00   58.9 47799.10199568     -4482.5049850590 -5.17E+01
     9 Pulay/Diag. 0.20E+00   59.9 42678.37923542     -4460.2090853173  2.23E+01
    10 Pulay/Diag. 0.20E+00   58.6 29018.77397837     -4448.4858203716  1.17E+01
    11 Pulay/Diag. 0.20E+00   60.1 30422.75295948     -4458.1250435109 -9.64E+00
    12 Pulay/Diag. 0.20E+00   58.8 20157.27665011     -4462.7197837500 -4.59E+00
    13 Pulay/Diag. 0.20E+00   60.2 20697.03326037     -4465.4866843212 -2.77E+00
    14 Pulay/Diag. 0.20E+00   58.6 14035.03955462     -4464.6656749474  8.21E-01
    15 Pulay/Diag. 0.20E+00   59.8 13859.56913168     -4455.4582585163  9.21E+00
    16 Pulay/Diag. 0.20E+00   58.6  9844.63604592     -4439.6169244281  1.58E+01
    17 Pulay/Diag. 0.20E+00   59.7  9086.46419396     -4429.7590093298  9.86E+00
    18 Pulay/Diag. 0.20E+00   59.0  6252.68491596     -4451.0446941090 -2.13E+01
    19 Pulay/Diag. 0.20E+00   59.8  5836.44669985     -4446.6123587806  4.43E+00
    20 Pulay/Diag. 0.20E+00   58.7  4369.58978109     -4434.7404123014  1.19E+01
    21 Pulay/Diag. 0.20E+00   59.8  3709.18259540     -4422.7286506587  1.20E+01
    22 Pulay/Diag. 0.20E+00   58.8  2919.47259531     -4423.1759843663 -4.47E-01
    23 Pulay/Diag. 0.20E+00   59.8  2418.12012615     -4420.5319920017  2.64E+00
    24 Pulay/Diag. 0.20E+00   58.8  1984.95398922     -4419.3227006816  1.21E+00
    25 Pulay/Diag. 0.20E+00   60.0  1707.00425122     -4420.3727826353 -1.05E+00
    26 Pulay/Diag. 0.20E+00   59.0  1274.71842881     -4420.2666697595  1.06E-01
    27 Pulay/Diag. 0.20E+00   60.3  1417.13141141     -4425.4603136343 -5.19E+00
    28 Pulay/Diag. 0.20E+00   58.8  1104.03431671     -4418.0031624370  7.46E+00

I was wondering, if there is any guidance or suggestions on how to handle these energy fluctuations when using the aug-cc-pvtz basis set and WB97X-D XC-functional? Additionally, I noticed that runtimes are approximately 1 minute per SCF iteration, I was curious if there was any advice on how to improve this runtime? I've attached a sample SLURM submission script that I used to generate the results located in the attached .out file. Please let me know if there is any additional information that I can provide and I greatly appreciate the support that you and the community provide.

All my best,
Nick

On Tuesday, October 22, 2024 at 3:48:22 AM UTC-4 Jürg Hutter wrote:
Hi

you are missing the &HF section in your specification of the hybrid functional.
Libxc only covers the density functional part, see the many examples in the tests/QS
sections.

regards
JH

________________________________________
From: cp... at googlegroups.com <cp... at googlegroups.com> on behalf of Nicholas Laws <nichol... at gmail.com>
Sent: Monday, October 21, 2024 4:14 PM
To: cp2k
Subject: [CP2K:20794] All-electron Geometry Optimization of EMIBF4

Hi all,

I am trying to do a geometry optimization for energy minimization of EMIBF4 using the aug-cc-pvtz basis set (attached below) and WB97X-D XC-functional. It seems that my optimization requires hundreds of SCF steps before convergence (as seen in the attached .out file) and I was wondering if there are any recommendations for doing all-electron geometry optimizations, especially for the one I discuss in this post (current implementation can be viewed in the attached .inp file)? Please let me know if there any additional information that I can clarify.

Thank you, and I look forward to hearing from you.

All my best,
Nick

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