# [CP2K:10533] Huge difference in adsorption energies between CP2K and VASP with PBE

Sharma SRK Chaitanya Yamijala sharma... at gmail.com
Mon Jul 16 18:07:29 UTC 2018

```Dear Prof. Hutter,

Thank you very much for your help. Following the last equations which you
wrote for energy, I have E1(uncorrected adsorption energy) = -0.863 eV and
E2 (counterpoise correction) = +1.0669. So, from the way the BSSE corrected
adsorption energy is defined, I am getting *+0.204 eV* which suggests that
the *adsorption is thermodynamically not feasible*. I am getting negative
values with VASP and FHIAIMS.

However, I would like to point that, when I consider the results of a BSSE
calculation (majorly the one-body contribution results) and calculate
the counterpoise correction (E2 = ((4)-(5)) +((6)-(7))), then I obtain *zero
correction* to the adsorption energy (because the energy of 4 = 5 and 6 =
7). Even following eq13 of this
<http://vergil.chemistry.gatech.edu/notes/cp.pdf> document by Prof.
Sherrill, I am obtaining basically zero correction. Thus, I believe the
printed value of counterpoise correction in the CP2K output is (1 - 5 - 7)
and not ((4)-(5)) +((6)-(7))).

My runs with TZVP calculation are not finished yet and I will try to update
the results when they are finished. If you get time, could you please
suggest anything else which I may need to change in the input or anything
you feel suspicious in the input?

Here are the energies for all the terms which you have mentioned in the
earlier email.

System      Geometry from      Basis     Energy (eV)

1  A+B          A+B                    A+B      -267383.806
2      A               A                        A           -589.596
3      B               B                        B      -266793.347
4      A           A+B                        A           -589.596 (Take
the A geometry from A+B and do a single point calculation)
5      A           A+B                   A+B            -589.596 (From one
body contribution result of BSSE calculation)
6      B           A+B                       B       -266793.143 (Take the
B geometry from A+B and do a single point calculation)
7      B           A+B                   A+B       -266793.143 (From one
body contribution result of BSSE calculation)

Thanks,
Sharma.

--------------------------------------------------------------------
SRK *Chaitanya* Sharma, Yamijala.
http://www.bmwong-group.com/group-members/

On Sat, Jul 14, 2018 at 9:28 AM, <hut... at chem.uzh.ch> wrote:

> Hi
>
> assuming you did all calculations correctly, you should have the following
>
> System      Geometry from      Basis
>
> 1  A+B          A+B            A+B
> 2  A            A              A
> 3  B            B              B
> 4  A            A+B            A
> 5  A            A+B            A+B
> 6  B            A+B            B
> 7  B            A+B            A+B
>
> The uncorrected adsorption energy is     :  E1 = (1) - (2+3)
>
> Counterpoise correction energy is        :  E2 = ((4)-(5)) +((6)-(7))
>
> BSSE corrected adsorption energy is      :  Ea = E1 + E2
>
>
> E1 is too negative because of BSSE.
> Counterpoise correction is positive because larger basis stabilises
> systems.
> Typically the counterpoise correction is 0-50% of the non-corrected energy
> (depending on the system and the basis)
>
> regards
>
> Juerg
>
> --------------------------------------------------------------
> Juerg Hutter                         Phone : ++41 44 635 4491
> Institut für Chemie C                FAX   : ++41 44 635 6838
> Universität Zürich                   E-mail: hut... at chem.uzh.ch
> Winterthurerstrasse 190
> CH-8057 Zürich, Switzerland
> ---------------------------------------------------------------
>
> -----cp... at googlegroups.com wrote: -----
> From: "Sharma SRK Chaitanya Yamijala"
> Sent by: cp... at googlegroups.com
> Date: 07/14/2018 01:59AM
> Subject: Re: [CP2K:10528] Huge difference in adsorption energies between
> CP2K and VASP with PBE
>
> I just want to add that, the energy of the CO obtained through the one
> body contributions (listed in the output of a BSSE calculation) and the
> energy of the optimized CO (in the same cell size but without the slab) is
> found to be exactly the same. To me, this suggests the current basis should
> be accurate enough as one should expect a larger effect of the BSSE on CO
> rather than on slab (as slab contributes to the large portion of basis
> functions of the total system). Kindly, let me know if my logic is wrong.
>
>
>
>
>
> --------------------------------------------------------------------
> SRK Chaitanya Sharma, Yamijala.
> http://www.bmwong-group.com/group-members/
>
>
> On Fri, Jul 13, 2018 at 1:16 PM, Sharma SRK Chaitanya Yamijala <
> sharma... at gmail.com> wrote:
> And I believe the increase in the adsorption energy could be because of
> the non-ground-state geometry of the "slab" during the BSSE calculation.
> The slab's absolute energy when considered in the monomer basis (for the
> ground state geometry) is -9804.47553 au and it is -9804.468056 au for the
> geometry in the dimer configuration (i.e. for the slab geometry in the
> "slab + CO" optimized geometry).
>
>
>
>
>
> --------------------------------------------------------------------
> SRK Chaitanya Sharma, Yamijala.
> http://www.bmwong-group.com/group-members/
>
>
> On Fri, Jul 13, 2018 at 12:29 PM, Sharma SRK Chaitanya Yamijala <
> sharma... at gmail.com> wrote:
> Dear Prof. Hutter,
>
> I have performed the BSSE corrections and the results are given below.
> Clearly, the BSSE corrected interaction energy is huge (~ 1 eV). If I
> consider this CP-corrected energy as the adsorption energy (I have
> calculated adsorption energy as Eads = EAB - EA -EB), then it will be too
> off from the VASP (-0.466 eV) or FHIAIMs (-0.595 eV) results. As mentioned,
> without BSSE the calculated adsorption energy is -0.863 eV. All the
> energies given are with Grimme's-D3 dispersion. Kindly, let me know if you
>
> To check the accuracy of my basis set, I have started a run with TZVP
> basis (instead of DZVP) for adsorption energy calculation and I will update
> here.
>
> On a different note, the number of basis functions used for the
> calculation in FHIAIMS (6172) and CP2K (5660) is roughly the same.
>  ------------------------------------------------------------
> -------------------
>  -
>      -
>  -                                 BSSE RESULTS
>     -
>  -
>      -
>  -                 CP-corrected Total energy:        0.039208
>     -
>  -
>      -
>  -                       1-body contribution:    -9804.468056
>     -
>  -                       1-body contribution:      -21.667247
>     -
>  -
>      -
>  -                       2-body contribution:     9826.174511
>     -
>  -                 BSSE-free interaction energy:     9826.174511
>      -
>  ------------------------------------------------------------
> -------------------
>
> Thanks,
> Sharma.
>
>
>
>
>
> --------------------------------------------------------------------
> SRK Chaitanya Sharma, Yamijala.
> http://www.bmwong-group.com/group-members/
>
>
> On Fri, Jul 13, 2018 at 12:31 AM,  <hut... at chem.uzh.ch> wrote:
> Hi
>
>  you are using a DZVP basis, this is rather small. Check the number
>  of basis functions. Do the same for the FHIaims calculation
>  and compare.
>  The cutoff of VASP cannot be compared to a local basis set.
>
>  regards
>
>  Juerg Hutter
>  --------------------------------------------------------------
>  Juerg Hutter                         Phone : ++41 44 635 4491
>  Institut für Chemie C                FAX   : ++41 44 635 6838
>  Universität Zürich                   E-mail: hut... at chem.uzh.ch
>  Winterthurerstrasse 190
>  CH-8057 Zürich, Switzerland
>  ---------------------------------------------------------------
>
>  -----cp... at googlegroups.com wrote: -----
>  To: "cp2k" <cp... at googlegroups.com>
>  From: "Sharma SRK Chaitanya Yamijala"
>  Sent by: cp... at googlegroups.com
>  Date: 07/12/2018 07:55PM
>  Subject: Re: [CP2K:10514] Huge difference in adsorption energies between
> CP2K and VASP with PBE
>
>
>  Dear Prof. Hutter,
>
>  Thanks. I will try the BSSE correction with CP2K. Regarding k-point
> sampling, in both the softwares, I have used Gamma point only. Could you
> please elobarate your point on "size of basis sets" here? I don't know how
> should I compare VASP basis (plane waves) with CP2K (both PW and
> Gaussians)? I have converged the CUTOFFs in both the cases such that the
> energy differences are < 1 meV.
>
>  Also, yesterday, I have performed similar calculations with FHIAims and I
> have obtained the adsorption energy (withOUT dispersion and BSSE
> corrections) as 0.412 eV which is again closer to the VASP result and to
> the result in the reference.
>
>
>  Thanks,
>  Sincerely,
>  Sharma.
>
>  On Thursday, July 12, 2018 at 12:11:59 AM UTC-7, jgh wrote:Hi
>
>  my first guess: you didn't calculate the BSSE correction.
>
>  other possible contributions: size of basis sets
>                                k-point sampling
>
>  regards
>
>  Juerg Hutter
>  --------------------------------------------------------------
>  Juerg Hutter                         Phone : ++41 44 635 4491
>  Institut für Chemie C                FAX   : ++41 44 635 6838
>  Universität Zürich                   E-mail: hut... at chem.uzh.ch
>  Winterthurerstrasse 190
>  CH-8057 Zürich, Switzerland
>  ---------------------------------------------------------------
>
>  -----cp... at googlegroups.com wrote: -----
>  From: "Sharma SRK Chaitanya Yamijala"
>  Sent by: cp... at googlegroups.com
>  Date: 07/12/2018 01:48AM
>  Subject: [CP2K:10507] Huge difference in adsorption energies between CP2K
> and VASP with PBE
>
>  Dear CP2K members,
>
>  I am calculating the adsorption energies of CO on ZnO (4x4-slab with 4
> layers of ZnO(10-10) surface). The adsorption energy obtained from VASP is
> ~ 0.3 eV (without dispersion) and it is ~ 0.45 eV (with
> dispSECTION_PARAMETERS TRUEersion). However, when calculating the same
> system with CP2K (geometry is re-optimized), I am obtaining the energies
> 0.688 eV and 0.863 eV for without and with dispersion correction,
> respectively.
>
>  The literature value is close to the VASP result. Here is the reference
> (kindly, see Table 2, C-down, 2x1 cell, Full).
>
>  B Meyer and D Marx 2003 J. Phys.: Condens. Matter 15 L89
>  http://iopscience.iop.org/article/10.1088/0953-8984/15/2/112/pdf
>
>  Could anyone give an advice on why there is such a discrepancy in the
> adsorption energies irrespective of using the same functional?
>
>  I am attaching the geometry and the input file for your reference.
>
>  Thanks,
>  Sharma.
>
>  --------------------------------------------------------------------
>  SRK Chaitanya Sharma, Yamijala.
>  http://www.bmwong-group.com/group-members/
>
>
>    --
>   You received this message because you are subscribed to the Google
> Groups "cp2k" group.
>   To unsubscribe from this group and stop receiving emails from it, send
> an email to cp2k+... at googlegroups.com.
>   To post to this group, send email to cp... at googlegroups.com.
>   Visit this group at https://groups.google.com/group/cp2k.
>   For more options, visit https://groups.google.com/d/optout.
>
>
>  [attachment "1CO_on_opt_4x4_slab.xyz" removed by Jürg Hutter/at/UZH]
>  [attachment "zno_bulk.inp" removed by Jürg Hutter/at/UZH]
>
>    --
>   You received this message because you are subscribed to the Google
> Groups "cp2k" group.
>   To unsubscribe from this group and stop receiving emails from it, send
> an email to cp2k+uns... at googlegroups.com.
>
>  To post to this group, send email to cp... at googlegroups.com.
>   Visit this group at https://groups.google.com/group/cp2k.
>   For more options, visit https://groups.google.com/d/optout.
>
>
>  --
>  You received this message because you are subscribed to a topic in the
>  To unsubscribe from this topic, visit https://groups.google.com/d/
> topic/cp2k/tjXJMpIfVx8/unsubscribe.
>  To unsubscribe from this group and all its topics, send an email to
>  To post to this group, send email to cp... at googlegroups.com.
>  Visit this group at https://groups.google.com/group/cp2k.
>  For more options, visit https://groups.google.com/d/optout.
>
>
>
>
>   --
>  You received this message because you are subscribed to the Google Groups
> "cp2k" group.
>  To unsubscribe from this group and stop receiving emails from it, send an
> email to cp2k+uns... at googlegroups.com.
>  To post to this group, send email to cp... at googlegroups.com.
>  Visit this group at https://groups.google.com/group/cp2k.
>  For more options, visit https://groups.google.com/d/optout.
>
>
> --
> You received this message because you are subscribed to a topic in the
> To unsubscribe from this topic, visit https://groups.google.com/d/
> topic/cp2k/tjXJMpIfVx8/unsubscribe.
> To unsubscribe from this group and all its topics, send an email to