[CP2K-user] [CP2K:21253] Broken Simmetry NEL

[lorenzo briccolani]

Dear Matthias,

Thank you very much for your help, as always—it is greatly appreciated.

Just to ensure I fully understand, the first column of values defines the
target orbital, while the second column corresponds to the initial orbital.
Therefore, in the case of the alpha electron, I add one electron with
spin-up (NEL +1) in the 3d orbital by removing it from the 4s orbital. For
the beta electron, I do not add any electron (NEL -1), transferring it from
the 4s to the 3d orbital.

I apologize if I seem insistent, but I would like to clarify this point, as
the manual refers to a single real value.

Following your recommendations, I assigned an initial multiplicity of two
to the Cu atom. However, I am unsure why the calculation still assigns 10
valence electrons overall, while for the beta electrons, it assigns 4.5
instead of 4. Because the values enclosed in square brackets, I believe,
refer to the number of alpha or beta electrons contained in each orbital.
This is why, in the case of beta electrons, I expected D 4.00 instead of
4.50. Below, I have included the relevant lines from the output:
Guess for atomic kind: Cu

 Electronic structure
    Total number of core electrons
18.00
    Total number of valence electrons
 10.00
    Total number of electrons
 28.00
    Multiplicity
doublet
    Alpha Electrons
    S   [  1.00  1.00  1.00]
    P   [  3.00  3.00]
    D      5.00
    Beta Electrons
    S   [  1.00  1.00  1.00]
    P   [  3.00  3.00]
    D      4.50

Best Regards

Lorenzo Briccolani

On Wed, 5 Mar 2025 at 12:02, Krack Matthias <matthias.krack at psi.ch> wrote:

> Dear Lorenzo
>
>
>
> The valence electron configuration of the Cu-q11 pseudopotential employed
> by you is 3d10 4s1. The following &BS section should create an initial 3d9
> doublet configuration for a Cu(2+) atom:
>
>
>
>  UKS
>
>   MULTIPLICITY 2
>
>
>
>   &BS
>
>     &ALPHA
>
>       N    3  4
>
>       L    2  0
>
>       NEL +1 -1
>
>     &END ALPHA
>
>     &BETA
>
>      N    3  4
>
>       L    2  0
>
>       NEL -1 -1
>
>     &END BETA
>
>   &END BS
>
> Note that these BS setting affects only the electron configuration of the
> initial atomic guess and the converged result might differ.
>
>
>
> HTH
>
>
>
> Matthias
>
>
>
> *From: *cp2k at googlegroups.com <cp2k at googlegroups.com> on behalf of
> lorenzo briccolani <lore.bricco.184 at gmail.com>
> *Date: *Tuesday, 4 March 2025 at 19:29
> *To: *cp2k <cp2k at googlegroups.com>
> *Subject: *[CP2K:21245] Broken Simmetry NEL
>
> Dear Users,
>
> I am reaching out as I am uncertain about the correct assignment of NEL
> values in the BS routine. The system under investigation consists of a
> molecule with a central Cu2+ atom coordinating two ligands in a square
> planar geometry. In a standard spin density calculation (UPBE/DZVP-MOLOPT)
> with a multiplicity of two, the spin densities are well reproduced, with
> the unpaired electron localized precisely on the copper atom. The Hirshfeld
> output reports the following values:
>
> Element  Kind  Ref Charge     Population       Spin moment  Net charge
>            Cu     4      11.000        6.182   5.514            0.668
> -0.695
>
> My objective is to replicate this result using the BS approach. For a Cu2+
> ion, I assume the configuration should be as follows:
> &KIND Cu
>      &BS ON
>       &ALPHA
>        L = 0 2
>        N = 4 3
>       NEL = -2 ?
>       &END
>       &BETA
>        L = 0 2
>        N = 4 3
>       NEL = -2 ?
>       &END
>      &END
>
> I have conducted several tests; however, I am unable to obtain the correct
> number of valence electrons and the expected multiplicity in the output. I
> have attached the input file for reference (opt.inp).
>
> I would be sincerely grateful for any suggestions regarding the
> appropriate assignment of the NEL values.
>
> Best regards,
>
> Lorenzo Briccolani
>
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