[CP2K-user] [CP2K:17925] understanding BSSE print out

[Victor Volkov]

Good morning Matthias:
here, is the result of BSSE application for the case when CP2K suggests a
relatively optimal adsorption
of a heterocycle molecule at interface.

After including BSSE, it is not too clear how to operate with the computed
numbers:
 -BSSE RESULTS                                -
-CP-corrected Total energy:     -455.120393
                                                  -
-1-body contribution:      -44.966343                  -
-1-body contribution:     -410.139056                  -
-2-body contribution:       -0.014995                  -
-BSSE-free interaction energy:       -0.014995

because if the BSSE free interaction is -0.014995 Hartree = -39.3693725
kJ/mol.

This is a huge number,
which is significantly larger that any typical binding
for single cycle aromatic molecules at carbonaceous materials.

Curiously,
the energies of binding by CP2K without BSSE agree with experimental
results relatively well.

Would the result (after BSSE inclusion) suggest that CP2K theory
is not yet fit to address the physics:
that a reasonable agreement without BSSE should be considered as a blind
coincidence,
and that CP2K would need further improvements?

Thank you for any comment.

In any way,
schönes wochenende.
:-)
With best,
Victor


On Wed, Oct 19, 2022 at 3:27 PM Krack Matthias (PSI) <matthias.krack at psi.ch>
wrote:

> Hi Victor
>
>
>
> As you wrote already, you need to add for each atomic kind the
> corresponding &KIND section for the GHOST kind like
>
>
>
> &KIND C_ghost
>
> BASIS_SET DZVP-MOLOPT-GTH
>
> GHOST
>
> &END KIND
>
>
>
> to get reasonable results.
>
> Usually, one is interested in the last number, the “BSSE-free interaction
> energy” which is here the difference of the total energies from run (5) and
> runs (3) and (4), i.e. (5) – [(3) + (4)]. A positive value implies a
> repulsive interaction (no binding) after removing the BSSE via the
> counterpoise (CP) correction.
>
>
>
> HTH
>
>
>
> Matthias
>
>
>
> *From: *cp2k at googlegroups.com <cp2k at googlegroups.com> on behalf of Victor
> Volkov <volkovskr at gmail.com>
> *Date: *Wednesday, 19 October 2022 at 13:00
> *To: *cp2k at googlegroups.com <cp2k at googlegroups.com>
> *Subject: *Re: [CP2K:17902] understanding BSSE print out
>
> Dear Matthias:
>
> thank you for the kind reply.
>
> I did not wish to be "too specific" about the system in public because the
> results are under
>
> a peer review.
>
> Here I attach one of the exemplary cases: pyridazine at graphene.
>
> Thank you.
>
> With best regards,
>
> Victor
>
>
>
>
>
> On Wed, Oct 19, 2022 at 12:12 PM Krack Matthias (PSI) <
> matthias.krack at psi.ch> wrote:
>
> Hi Victor
>
>
>
> Without the full input, it is difficult to make any suggestion. Do you
> have a &BSSE section defining the FRAGMENTS?
>
>
>
> Best
>
>
>
> Matthias
>
>
>
> *From: *cp2k at googlegroups.com <cp2k at googlegroups.com> on behalf of Victor
> Volkov <volkovskr at gmail.com>
> *Date: *Saturday, 15 October 2022 at 19:53
> *To: *cp2k <cp2k at googlegroups.com>
> *Subject: *[CP2K:17873] understanding BSSE print out
>
> Dear members:
>
> good evening/morning.
>
>
>
> it is not clear to me how to interpret CP2K print out for BSSE.
>
>
>
> If I take a small guest (like benzene) next to a carbon layer using
> GWP/PBE/DZVP
>
> Of course, since interactions are so week, DFTD3 is a must - otherwise a
> benzene may "fly away".
>
>
>
> Then, using BSSE  for S1(guest) and S2 (carbon layer)
>
> CP2K prints
>
> S1 + S2ghost: Total energy -455.12112693238430 Hartree
> S1ghost + S2: Total energy -455.12112693238430 Hartree
> S1           + S2: Total energy -455.12112693238441 Hartree
>
>
>
> The differences are none or tiny.
>
>
>
> However, the final print is:
>
> CP-corrected Total energy:        0.015729
> 1-body contribution:                 -44.96634268204556
> 1-body contribution:                -410.13905550190344
> 2-body contribution:                 455.121127
> BSSE-free interaction energy:      455.121127
>
>
>
> *First, it is not clear what is "CP".*
>
>
>
> Next, i*f this is the value of the BSSE artifact* (due to the
> wave-function truncation),
>
> then *its huge* 41.2964895 kJ/mole.
>
> This would be *almost twice larger than the binding energy* of
> benzene-like guests when at carbonaceous surfaces.
>
> This would mean that quality evaluations of binding energies for such
> systems using CP2K would be very difficult.
>
>
>
> Any comments to hear would be nice.
>
>
>
> Finally, it is not clear why 2-body contribution and* BSSE-free
> interaction are printed as positive numbers*.
>
>
>
> I hope the questions I ask be interesting for users and helpful for the
> on-line manual to update.
>
>
>
> After all, I wish to note that it was by a *rare chance I was able to
> track* the old
>
> notice *on the importance of declaring*
>
>     &KIND X_ghost
>      BASIS_SET DZVP-MOLOPT-SR-GTH
>      GHOST
>     &END KIND
>
>
>
> Even though ...
>
> *if I skip such definition, the numbers would come "a bit better"*
>
> *:-)*
>
> CP would be about 21 kJ/mole, what is about comparable to the binding
> energy
>
> of a benzene-like guest to a carbonaceous material.
>
>
>
> Thank you for your time and attention.
>
>
>
> I wish everybody be well and happy.
>
>
>
> Victor
>
>
>
>
>
>
>
>
>
>
>
>
>
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