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<p class="MsoNormal"><span lang="DE-CH" style="font-size:11.0pt;mso-fareast-language:EN-US">Dear Lorenzo<o:p></o:p></span></p>
<p class="MsoNormal"><span lang="DE-CH" style="font-size:11.0pt;mso-fareast-language:EN-US"><o:p> </o:p></span></p>
<p class="MsoNormal"><span lang="EN-US" style="font-size:11.0pt;mso-fareast-language:EN-US">Sorry, my suggestion for the &BS section was wrong, try this instead<o:p></o:p></span></p>
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</span><span lang="IT-CH" style="font-size:11.0pt;font-family:Consolas;color:#212121">&BS</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="IT-CH" style="font-size:11.0pt;font-family:Consolas;color:#212121"> &ALPHA</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="IT-CH" style="font-size:11.0pt;font-family:Consolas;color:#212121"> N 3 4</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="IT-CH" style="font-size:11.0pt;font-family:Consolas;color:#212121"> L 2 0</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="IT-CH" style="font-size:11.0pt;font-family:Consolas;color:#212121"> NEL 0 -1</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="IT-CH" style="font-size:11.0pt;font-family:Consolas;color:#212121">
</span><span lang="EN-US" style="font-size:11.0pt;font-family:Consolas;color:#212121">&END ALPHA</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas;color:#212121"> &BETA</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas;color:#212121"> N 3 4</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas;color:#212121"> L 2 0</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas;color:#212121"> NEL -2 -1</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas;color:#212121"> &END BETA</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas;color:#212121"> &END BS</span><span style="color:#212121"><o:p></o:p></span></p>
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<span lang="EN-US" style="font-size:11.0pt;mso-fareast-language:EN-US"><o:p> </o:p></span></p>
<p class="MsoNormal"><span lang="EN-US" style="font-size:11.0pt;mso-fareast-language:EN-US">Best<o:p></o:p></span></p>
<p class="MsoNormal"><span lang="EN-US" style="font-size:11.0pt;mso-fareast-language:EN-US"><o:p> </o:p></span></p>
<p class="MsoNormal"><span lang="EN-US" style="font-size:11.0pt;mso-fareast-language:EN-US">Matthias<o:p></o:p></span></p>
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<b><span style="color:black">From: </span></b><span style="color:black">cp2k@googlegroups.com <cp2k@googlegroups.com> on behalf of lorenzo briccolani <lore.bricco.184@gmail.com><br>
<b>Date: </b>Wednesday, 5 March 2025 at 19:54<br>
<b>To: </b>cp2k@googlegroups.com <cp2k@googlegroups.com><br>
<b>Subject: </b>Re: [CP2K:21253] Broken Simmetry NEL<o:p></o:p></span></p>
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<p class="MsoNormal" style="margin-left:36.0pt">Dear Matthias,<br>
<br>
Thank you very much for your help, as always—it is greatly appreciated.<br>
<br>
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.<br>
<br>
I apologize if I seem insistent, but I would like to clarify this point, as the manual refers to a single real value.<br>
<br>
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:<br>
Guess for atomic kind: Cu<br>
<br>
Electronic structure<br>
Total number of core electrons 18.00<br>
Total number of valence electrons 10.00<br>
Total number of electrons 28.00<br>
Multiplicity doublet<br>
Alpha Electrons<br>
S [ 1.00 1.00 1.00]<br>
P [ 3.00 3.00]<br>
D 5.00<br>
Beta Electrons<br>
S [ 1.00 1.00 1.00]<br>
P [ 3.00 3.00]<br>
D 4.50<br>
<br>
Best Regards <br>
<br>
Lorenzo Briccolani<o:p></o:p></p>
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<p class="MsoNormal" style="margin-left:36.0pt"><o:p> </o:p></p>
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<p class="MsoNormal" style="margin-left:36.0pt">On Wed, 5 Mar 2025 at 12:02, Krack Matthias <<a href="mailto:matthias.krack@psi.ch">matthias.krack@psi.ch</a>> wrote:<o:p></o:p></p>
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<span lang="DE-CH" style="font-size:11.0pt">Dear Lorenzo</span><o:p></o:p></p>
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<span lang="DE-CH" style="font-size:11.0pt"> </span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt">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:</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> </span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> UKS</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> MULTIPLICITY 2</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt"> </span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> &BS</span><o:p></o:p></p>
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<span lang="IT-CH" style="font-size:11.0pt;font-family:Consolas"> &ALPHA</span><o:p></o:p></p>
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<span lang="IT-CH" style="font-size:11.0pt;font-family:Consolas"> N 3 4</span><o:p></o:p></p>
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<span lang="IT-CH" style="font-size:11.0pt;font-family:Consolas"> L 2 0</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> NEL +1 -1</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> &END ALPHA</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> &BETA</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> N 3 4</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> L 2 0</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> NEL -1 -1</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> &END BETA</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt;font-family:Consolas"> &END BS</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt">Note that these BS setting affects only the electron configuration of the initial atomic guess and the converged result might differ.</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt"> </span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt">HTH</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt"> </span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt">Matthias</span><o:p></o:p></p>
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<span lang="EN-US" style="font-size:11.0pt"> </span><o:p></o:p></p>
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<b><span style="color:black">From: </span></b><span style="color:black"><a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a> <<a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a>> on behalf of lorenzo
briccolani <<a href="mailto:lore.bricco.184@gmail.com" target="_blank">lore.bricco.184@gmail.com</a>><br>
<b>Date: </b>Tuesday, 4 March 2025 at 19:29<br>
<b>To: </b>cp2k <<a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a>><br>
<b>Subject: </b>[CP2K:21245] Broken Simmetry NEL</span><o:p></o:p></p>
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Dear Users, <br>
<br>
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:<br>
<br>
Element Kind Ref Charge Population Spin moment Net charge<br>
Cu 4 11.000 6.182 5.514 0.668 -0.695<br>
<br>
My objective is to replicate this result using the BS approach. For a Cu2+ ion, I assume the configuration should be as follows:<br>
&KIND Cu<br>
&BS ON<br>
&ALPHA<br>
L = 0 2<br>
N = 4 3<br>
NEL = -2 ?<br>
&END<br>
&BETA<br>
L = 0 2<br>
N = 4 3<br>
NEL = -2 ? <br>
&END<br>
&END<br>
<br>
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).<br>
<br>
I would be sincerely grateful for any suggestions regarding the appropriate assignment of the NEL values.<br>
<br>
Best regards,<br>
<br>
Lorenzo Briccolani <o:p></o:p></p>
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