<div dir="ltr">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</div> <div class="gmail_quote gmail_quote_container"><div dir="ltr" class="gmail_attr">On Wed, 5 Mar 2025 at 12:02, Krack Matthias <<a href="mailto:matthias.krack@psi.ch">matthias.krack@psi.ch</a>> wrote: </div><blockquote class="gmail_quote" style="margin:0px 0px 0px 0.8ex;border-left:1px solid rgb(204,204,204);padding-left:1ex"><div class="msg3299884395211380643"> <div lang="en-CH" style="overflow-wrap: break-word;"> <div class="m_3299884395211380643WordSection1"> 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 <div id="m_3299884395211380643mail-editor-reference-message-container"> <div> <div> <div style="border-right:none;border-bottom:none;border-left:none;border-top:1pt solid rgb(181,196,223);padding:3pt 0cm 0cm"> From: <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>> Date: Tuesday, 4 March 2025 at 19:29 To: cp2k <<a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a>> Subject: [CP2K:21245] Broken Simmetry NEL </div> 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 -- 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 <a href="mailto:cp2k+unsubscribe@googlegroups.com" target="_blank">cp2k+unsubscribe@googlegroups.com</a>. To view this discussion visit <a href="https://groups.google.com/d/msgid/cp2k/7b7ad053-f176-49f2-a9ea-0580b9d0d584n%40googlegroups.com?utm_medium=email&utm_source=footer" target="_blank"> https://groups.google.com/d/msgid/cp2k/7b7ad053-f176-49f2-a9ea-0580b9d0d584n%40googlegroups.com</a>. </div> </div> </div> </div> </div> -- 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 <a href="mailto:cp2k+unsubscribe@googlegroups.com" target="_blank">cp2k+unsubscribe@googlegroups.com</a>. To view this discussion visit <a href="https://groups.google.com/d/msgid/cp2k/ZRAP278MB08276547DC4F2701A2644E5EF4CB2%40ZRAP278MB0827.CHEP278.PROD.OUTLOOK.COM?utm_medium=email&utm_source=footer" target="_blank">https://groups.google.com/d/msgid/cp2k/ZRAP278MB08276547DC4F2701A2644E5EF4CB2%40ZRAP278MB0827.CHEP278.PROD.OUTLOOK.COM</a>. </div></blockquote></div> -- 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 <a href="mailto:cp2k+unsubscribe@googlegroups.com">cp2k+unsubscribe@googlegroups.com</a>. To view this discussion visit <a href="https://groups.google.com/d/msgid/cp2k/CAJPdbE-4Apgw%3DoyYG-LT%2BmkkwVrMJmfEw29VQ9VVqohHoCF85A%40mail.gmail.com?utm_medium=email&utm_source=footer">https://groups.google.com/d/msgid/cp2k/CAJPdbE-4Apgw%3DoyYG-LT%2BmkkwVrMJmfEw29VQ9VVqohHoCF85A%40mail.gmail.com</a>.