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<TITLE>CuO, LDA+U, Pseudopots, etc.</TITLE>
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<P DIR=LTR><SPAN LANG="en-us"><FONT FACE="Calibri">To All (especially Paolo, Nicola, Matteo and Axel):</FONT></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"><FONT FACE="Calibri">I</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">m in the middle of attempting, as an exercise,</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">the</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">calculation of the</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">electronic structure of monoclinic CuO (tenorite)</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">within the LDA+U provisions of PWscf</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> (Cu is on the</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">“</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">approved list</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">”</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"></FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">of elements</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">contained in set</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">_hubbard_l.f90 and</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">tabd.f90)</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">. FeO and NiO I get to go OK, but CuO</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> is giving me problems. Tenorite is a well-</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">established</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"></FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">AF Hubbard-type insulator, and</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">the LDA+U approach</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">can yield a</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"></FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">supportive</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> band structure</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> (e.g., see</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">JPCM 11</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">, 5021 (1999) and references therein</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">).</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> </FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">However, I am not aware of an</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> LDA+U calculation starting from</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">a PW/PP</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">formalism</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> for tenorite. If one exists, please send me the reference and ignore the rest of this posting.</FONT></SPAN><SPAN LANG="en-us"></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"><FONT FACE="Calibri">Simplistically, the initial</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">d-state</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">configur</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">ation of Cu2+ in CuO by Hund</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">s Rule should be</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">3d9</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> (one empty minority spin state state</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">…</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">a hole). </FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri"></FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">But, with nspin=2, lda_plus_u set true, and U=5 eV (arbitrary)</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">, the initial minority spin occupation</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">gets</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> set to unity, not</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">4</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">/5 on average</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> (3/5 for Ni and 1/5 for Fe)</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">. Is this due to occ_loc being set to 10 in tabd.f90 and not 9</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">(it</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">s 6 for Fe and 8 for Ni)? The occupation</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> distribution converges to around 0.92 for eg and 0.99</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> for t2g with self-consistency</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">, a metallic state,</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> and no amount of</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">“</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">alternat</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">iv</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">e user ns</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"></FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">eigenvalue</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">guidance</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">”</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"></FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">gives a gap</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">. I haven</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">t tried any Wannier projection</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">s</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">…</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">rich man</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">s or poor</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">…</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">yet, because I suspect there is another issue</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">…</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">choice of the proper Cu PP.</FONT></SPAN><SPAN LANG="en-us"></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"><FONT FACE="Calibri">The choice of Cu pseudopotentia</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">ls available in the PWscf library are rather limited and weird</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">…</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">at least to my</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">naïve</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"></FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">and limited experience. I have been using primarily the Perdew-Zunger</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri"></FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">LDA</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">PP, Cu.</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">pz-n-van_ak.UPF</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">, computed with valence orbital occupations</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">3d9.5, 4s1.0 and</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">4p0.5 (!)</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> (the PW91</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">and PBE</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">functional</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">s</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"></FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">have</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> equivalent occupations and give similar results</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">). When I try Cu.</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri">pz-d-rrkjus.UPF, with 3d10,</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">4s1</FONT></SPAN><SPAN LANG="en-us"><FONT FACE="Calibri"> and 4p-1(!!!), the first scf iteration yields individual spin occupations</FONT></SPAN><SPAN LANG="en-us"> <FONT FACE="Calibri">of nearly 5(!!!), and the situation gets really ugly thereafter.</FONT></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">Why aren</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">t there Cu PPs with occupation</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">s 3d10, 4s1, or even 3d9, 4s2</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">?</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri"> I</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">ve spent the afternoon</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"> <FONT SIZE=2 FACE="Calibri">studying Paolo</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">s guide to PP generation and</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"> <FONT SIZE=2 FACE="Calibri">would</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri"> be willing to give these a try if that would help</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">…</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">but I sorely need some advice.</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri"> I</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">ve also been looking over David Vanderbilt</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">s web si</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">t</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">e and found this bit of wisdom</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">:</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri"> </FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"> <FONT SIZE=2 FACE="Calibri">“</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">Choosing the method of pseudizing the local potential</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">…This is something of a black art</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">”</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">.</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">-Paul</FONT></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">PS</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">…</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">there is something truly marvelous and mysterious about the CuO double bond</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">…</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">it</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">s given us high temperature superconductivity</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">. But 21 years later, there</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">’</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">s no general agreement</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"> <FONT SIZE=2 FACE="Calibri">on</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"> <FONT SIZE=2 FACE="Calibri">wherein</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri"> and why</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri"> it arises</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">.</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">PPS</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">…</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri">Is there a utility</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri"> somewhere</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><FONT SIZE=2 FACE="Calibri"> that plots the radial dependence of</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"> <FONT SIZE=2 FACE="Calibri">V(r) and/or rho(r) of a given PP?</FONT></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"><B><I></I></B></SPAN><SPAN LANG="en-us"><B><I></I></B></SPAN><SPAN LANG="en-us"><B><I></I></B></SPAN><B><I><SPAN LANG="en-us"><FONT SIZE=4 FACE="Comic Sans MS">Paul M. Grant, PhD</FONT></SPAN></I></B><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"><B></B></SPAN><SPAN LANG="en-us"><B></B></SPAN><SPAN LANG="en-us"><B></B></SPAN><B><SPAN LANG="en-us"><FONT SIZE=2 FACE="Arial">Principal, W2AGZ Technologies</FONT></SPAN></B><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"><B></B></SPAN><SPAN LANG="en-us"><B></B></SPAN><SPAN LANG="en-us"><B></B></SPAN><B><SPAN LANG="en-us"><FONT SIZE=2 FACE="Arial">Visiting Scholar, Applied Physics, Stanford University</FONT></SPAN></B><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"><B></B></SPAN><SPAN LANG="en-us"><B></B></SPAN><SPAN LANG="en-us"><B></B></SPAN><B><SPAN LANG="en-us"><FONT SIZE=2 FACE="Arial">EPRI Science Fellow (Retired)</FONT></SPAN></B><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN></P>
<P DIR=LTR><SPAN LANG="en-us"><B></B></SPAN><SPAN LANG="en-us"><B></B></SPAN><SPAN LANG="en-us"><B></B></SPAN><B><SPAN LANG="en-us"><FONT SIZE=2 FACE="Arial">IBM Research Staff Member Emeritus</FONT></SPAN></B><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN><SPAN LANG="en-us"></SPAN></P>
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