[CP2K-user] [CP2K:21205] Re: Counterpoise correction with Grimme D4

[Holger Sassnick]

Hi,

thank you for the valuable advice, I will read myself into the topic and 
check out the different approaches.

All the best,
Holger

Jürg Hutter schrieb am Montag, 24. Februar 2025 um 11:40:06 UTC+1:

> Hi
>
> I assume that BSSE error is for the replacement of a single water within
> the solvated MOF. BSSE in water systems are rather difficult to avoid
> (see in the book of Koch & Holthausen pp 222/223).
>
> I assume you can get decent results using the original Molopt basis sets
> (in BASIS_MOLOPT - not sr types). Adding difuse sp functions would
> then go to the limit. However, this will cost CPU time.
>
> Another idea (empirical) would be to follow the work of Grimme on the -3c
> methods. There BSSE for small basis sets is corrected using a pair 
> potential.
> You would have to get the parameters (Basis set and functional dependent)
> yourself.
> For applying it, see examples in the tests folder, e.g.
> cp2k/tests/QS/regtest-hf-3c/*.inp
>
> regards
> JH
>
> ________________________________________
> From: cp... at googlegroups.com <cp... at googlegroups.com> on behalf of Holger 
> Sassnick <holger.... at gmail.com>
> Sent: Sunday, February 23, 2025 10:10 AM
> To: cp2k
> Subject: Re: [CP2K:21199] Re: Counterpoise correction with Grimme D4
>
> Hi Prof Hutter,
>
> in principle metalorganic frameworks with water adsorbed in the pores 
> (like the attached input file of the initial post). The BSSE here is around 
> 0.05 eV for one water molecule in the MOF. I am planning to train MLPs on 
> the total energies that are in turn used in Monte Carlo simulations and the 
> binding energy (MOF/H2O - MOF - H2O) is plugged into the criteria to accept 
> or reject a deletion/insertion move. So I think I really need to ensure 
> that the BSSE is very low in order to not bias the MC simulations.
>
> Taking that into account, I see two options:
> * Remove the BSSE via the Counterpoise correction on the whole training 
> set. This would mean a multitude of calculations for each training point.
> * Move to a plane-wave code.
>
> I very much like CP2K since it is a very efficient code with extensive 
> functionality. Thus, I was wondering whether it would be possible to have a 
> basis set with negligible BSSE in CP2K.
>
> All the best,
> Holger
>
> Jürg Hutter schrieb am Donnerstag, 20. Februar 2025 um 10:30:23 UTC+1:
> Hi
> What type of system and BSSE values are you interested in? There is
> a discussion on BSSE for Molopt basis sets in the original paper.
> Results are for small molecule dimers.
> See
> J. Chem. Phys. 127, 114105 (2007) https://doi.org/10.1063/1.2770708
> Section III D, Table VI
> Molopt basis sets outperform normal Gaussian basis sets. However,
> I don't know how the numerical basis sets look for these systems.
>
> regards
> JH
>
> ________________________________________
> From: cp... at googlegroups.com <cp... at googlegroups.com> on behalf of Holger 
> Sassnick <holger.... at gmail.com>
> Sent: Thursday, February 20, 2025 7:54 AM
> To: cp2k
> Subject: Re: [CP2K:21177] Re: Counterpoise correction with Grimme D4
>
> Hi Prof Hutter,
>
> Thank you for the reply and insights. Unfortunately, I fear that the 
> constant BSSE would still bias the sampling if the "binding energy" is part 
> of the acceptance criteria to insert/delete a molecule in a MC scheme.
> In FHI-Aims, (from my experience) even the larger basis sets seem to 
> perform satisfactorily on molecular as well as dense systems. Do you think 
> it would be worth a try to design, e.g., a QZVPP basis set to push the 
> boundaries a bit?
> I am not sure if that would be large enough to keep the BSSE on an 
> acceptable level.
>
> All the best,
> Holger
> Jürg Hutter schrieb am Mittwoch, 19. Februar 2025 um 11:58:30 UTC+1:
> Hi
>
> the MOLOPT basis sets are optimized to perform for a wide range of
> systems (molecules, solutes, solids, open structures), while keeping a
> small number of functions for performance reasons.
> BSSE is of similar size as for comparable size Gaussian basis sets.
> For MD calclulation we tested and confirm that BSSE is typically
> a constant shift on energies and does not affect dynamics.
> If you want to have smaller/no BSSE you have to increase the
> number of functions and e.g. include the atomic ground
> state functions in the Basis (as in FHI-AIMS). There is the danger
> that these near complete basis sets will perform poorly in dense
> systems due to bad condition numbers.
>
> regards
> JH
>
> ________________________________________
> From: cp... at googlegroups.com <cp... at googlegroups.com> on behalf of Holger 
> Sassnick <holger.... at gmail.com>
> Sent: Thursday, February 13, 2025 11:14 AM
> To: cp2k
> Subject: Re: [CP2K:21142] Re: Counterpoise correction with Grimme D4
>
> Hi Prof Hutter,
>
> thank you for transferring the issue to the github repository. I was also 
> wondering whether it would be reasonable and feasible to design a larger 
> MOLOPT basis set with negligible BSSE. In this context I am also thinking 
> about the training of MLPs, e.g. in this publication (
> https://pubs.acs.org/doi/10.1021/jacs.4c15287) trajectories were 
> re-calculated with VASP for the training to ensure accurate results.
>
> Fox example, in FHI-Aims the "tight" basis set parameters have hardly any 
> BSSE. I know that the code uses a different localized basis set, so maybe 
> this kind of accuracy cannot be reached with GTOs? I would be happy to hear 
> your opinion on this matter.
>
> All the best,
> Holger
>
>
> Jürg Hutter schrieb am Montag, 10. Februar 2025 um 09:39:16 UTC+1:
> Hi
>
> thank you for bringing this to our attention. I have opened a bug report
> on the CP2K github page.
> https://github.com/cp2k/cp2k/issues
> [CP2K:21126] Counterpoise correction with Grimme D4
>
> regards
> JH
>
> ________________________________________
> From: cp... at googlegroups.com <cp... at googlegroups.com> on behalf of Holger 
> Sassnick <holger.... at gmail.com>
> Sent: Monday, February 10, 2025 7:19 AM
> To: cp2k
> Subject: [CP2K:21130] Re: Counterpoise correction with Grimme D4
>
> Hi Quentin,
>
> Thank you for the help and the swift response. You are right, the 
> dispersion interaction of "ghost" atoms is (wrongly) added which leads to 
> these unreasonable values. As far as I understand, I can just manually sum 
> up the energy contributions of the fragments, replacing the dispersion 
> interaction energy with the one from the fragment without ghost atoms. 
> Taking those total energy and calculating the interaction energy and 
> BSSE-corrected total energy leads then to values similar to PBE or PBE-D3.
>
> I think it would be also great if the implementation in CP2K could take 
> care of ghost atoms and calculate all the fragment energies correctly as is 
> done for the Grimme-D3 and other van der Waals corrections.
>
> Have a great start to the week.
> All the best,
> Holger
>
> Quentin Pessemesse schrieb am Sonntag, 9. Februar 2025 um 01:54:45 UTC+1:
> Also, the order of magnitude of your "BSSE-corrected" interaction energy 
> looks like the order of magnitude of E(disp)AB, which would make sense if 
> the ghost atoms are not treated as ghost by the empirical dispersion 
> correction
>
> Le dimanche 9 février 2025 à 01:39:46 UTC+1, Quentin Pessemesse a écrit :
> Hi Holger,
> Counterpoise correction is a correction to the electronic energy, you 
> should reason only on the electronic energies. The dispersion energy of the 
> isolated fragments has no physical meaning, and the D3/D4 empirical 
> correctoin plays no part in the BSSE as it is added after the SCF, and only 
> depends on the geometry.
> Here, I think CP2k is giving dispersion correction to the ghost atoms, 
> calculating both the error that comes from basis functions of fragment 
> being used to build the density of fragment B (BSSE), and adding some 
> dispersion energy of the fragments and total system as well.
> Instead of :
> BSSE = (EA − EA(B)) + (EB − E (A)B)
> You get:
> ([E(elec)A + E(disp)A] - [E(elec)A(B) - E(disp)AB]) + ([E(elec)B + 
> E(disp)B] - [E(elec)(A)B - E(disp)AB]) = BSSE + (E(disp)A + E(disp)B - 
> 2*E(disp)AB)
> Try to run the BSSE single point calculation without the empirical 
> dispersion and substract it from the interaction energy you get with D3/D3 
> correction. If it does not fix the issue, maybe I'm mistaken and something 
> else is wrong.
> Hope this helped :)
> Q.
> Le samedi 8 février 2025 à 13:36:41 UTC+1, Holger Sassnick a écrit :
> Hello,
>
> lately I have been trying to calculate the adsorption energy of water in 
> the CAU-23 MOF with different XC functionals. To avoid the quite 
> significant BSSE of CP2K's MOLOPT basis sets, I had to apply a counterpoise 
> correction.
>
> However, when using the Grimme D4 method the obtained values didn't really 
> make sense as they resulted in a positive interaction energy (I have 
> attached the corresponding input and output files). The same calculation 
> with the PBE functional or PBE + Grimme D3 gives a negative interaction 
> energy (the absolute value is also significantly smaller).
>
> I was wondering whether this is a bug in the code? Would it be possible 
> that the ghost atoms are not properly treated by the interface to the DFTD4 
> library?
>
> I would be very grateful for some feedback.
>
> Thanks in advance and all the best,
> Holger
>
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