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Dear WIEN2k community and Prof. Blaha,<br>
</p>
<p style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
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<p style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
I am currently performing constrained DFT+U calculations on a 2x2x2 BaTiO3 supercell with an Fe dopant and an oxygen vacancy using WIEN2k 24.1. My ultimate goal is to systematically investigate all possible d-orbital electronic multiplets (following the methodology
in Dorado et al., PRB 79, 235125 (2009) and previous discussions on this mailing list by Bin Shao in 2015 <a href="http://zeus.theochem.tuwien.ac.at/pipermail/wien/2015-July/023196.html" target="_blank" rel="noopener noreferrer" class="x_OWAAutoLink" id="LPlnk833611" tabindex="-1" disabled="true">http://zeus.theochem.tuwien.ac.at/pipermail/wien/2015-July/023196.html</a> and
Jayangani in 2019 <a href="http://zeus.theochem.tuwien.ac.at/pipermail/wien/2019-July/029531.html" target="_blank" rel="noopener noreferrer" class="x_OWAAutoLink" id="LPlnk809763" tabindex="-1" disabled="true">http://zeus.theochem.tuwien.ac.at/pipermail/wien/2019-July/029531.html</a>).<br>
<br>
<b>The Core Issue:</b><br>
<br>
</p>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
I am observing a significant deviation (> 0.3 e-) between my explicitly constructed initial density matrix (<code>.dmatup/dn</code>), the IPDOS up to EF(Fe), and the final output density matrix obtained via <code>lapwdm</code>, even though the calculation converges
successfully and i haven't released the constraint.<br>
<br>
<div>To test the constraint, I intentionally chose a non-standard configuration to ensure I can apply constraints beyond estimated egt2g spliting:<br>
<br>
Target UP: Only dyz occupied (1.0)<br>
<br>
Target DN: dxy, dz2, dxz, dx2-y2 occupied (1.0 each)</div>
<br>
Here is a figure of the summary table of the discrepancies I observed:(with all smaller than 0.1 components ignored) <br>
<img naturalheight="65" naturalwidth="773" size="4227" id="img853134" tabindex="-1" style="max-width: 99.9%; user-select: none;" contextid="img325691" customtabindex="0" disabled="true" src="cid:13df257c-eac1-40c4-98fd-36f12ca211db"><br>
PS: I can only set d,dxy,dz2,dx2-y2,dxz+yz for this system in the qtl.<br>
<br>
(I also considered the local rotation matrix, but since they share the same rotation and the tetragonal Ti site is not severely distorted, I believe it cannot fully explain this large deviation.)<br>
<br>
Below are the full technical details of my setup. Any insights or suggestions on how to firmly "lock" these metastable states would be greatly appreciated.<br>
<div><b><br>
My Questions:</b><br>
large deviation while still constrained: I observe this huge discrepancy even before releasing the constraint. For example, my single dyz target was split into two ~0.85 occupations in .scfdmup. Does this imply that the system's symmetry is still actively forcing
a degeneracy between xz and yz?<br>
<br>
Normal behavior vs. Setup error: Is it normal to see such a large deviation between the setup .dmat and the output .scfdm while the orbital potential is still being actively applied, or does this indicate an error in my initialization/setup?<br>
<br>
Physical/Algorithmic interpretation: If my setup is perfectly fine, how should I understand what is happening here? Is the imposed U potential simply not strong enough to overcome the hybridization and SCF mixing, thereby "washing out" my imposed constraint
during the cycles?<br>
<br>
Alternative methods for a "hard lock": Are there other techniques to more rigidly lock the desired electronic multiplet? For instance, should I artificially increase the $U$ value during the initial SCF cycles?</div>
<br>
<div><b>ALL Technical Details:</b><br>
<br>
1. setup:</div>
<div>init_lapw -b -sp<br>
prepare .indm & .inorb & .dmatup/dn</div>
<div>x orb -up -p</div>
<div>x orb -dn -p</div>
<div>runsp_lapw -p -orbc -i 500 -ec 0.0001 -cc 0.001<br>
<br>
</div>
2. .indm:<br>
<br>
<div>-12. Emin cutoff energy</div>
<div> 1 number of atoms for which density matrix is calculated</div>
<div> 8 1 2 index of 1st atom, number of L's, L1</div>
<div> 0 0 r-index, (l,s)index</div>
<br>
3.<span style="font-family:Calibri,Helvetica,sans-serif,EmojiFont,"Apple Color Emoji","Segoe UI Emoji",NotoColorEmoji,"Segoe UI Symbol","Android Emoji",EmojiSymbols"> .inorb<br>
</span>
<div>1 1 0 nmod, natorb, ipr</div>
<div>PRATT 1.0 BROYD/PRATT, mixing</div>
<div> 8 1 2 iatom nlorb, lorb</div>
<div> 1 nsic 0..AMF, 1..SIC, 2..HFM</div>
<div> 0.37 0.07 U J (Ry)</div>
<br>
4. initial .dmatup(target dyz)<br>
<br>
<div> 8 atom density matrix</div>
<div><br>
</div>
<div> 2 0.000000 0.000000 0.000000 L, Lx,Ly,Lz in global orthogonal system</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00 1.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div><br>
</div>
<div> 0.0000000000000E+00 0.0000000000000E+00</div>
<br>
</div>
<span style="font-size:16px; font-family:Calibri,Helvetica,sans-serif,EmojiFont,"Apple Color Emoji","Segoe UI Emoji",NotoColorEmoji,"Segoe UI Symbol","Android Emoji",EmojiSymbols">5. initial .dmatdn(target dxy, dz2, dxz, dx2-y2</span><span style="font-size:16px; font-family:Calibri,Helvetica,sans-serif,EmojiFont,"Apple Color Emoji","Segoe UI Emoji",NotoColorEmoji,"Segoe UI Symbol","Android Emoji",EmojiSymbols">)<br>
</span><span style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px"></span>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
8 atom density matrix</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
2 0.000000 0.000000 0.000000 L, Lx,Ly,Lz in global orthogonal system</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
1.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
1.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00 1.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00 0.0000000000000E+00</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
<br>
</div>
<div style="font-family:Calibri,Helvetica,sans-serif,serif,EmojiFont; font-size:16px">
1.0000000000000E+00 0.0000000000000E+00<br>
<br>
6. Post-processing for IPDOS up to EF:<br>
<div>x lapw2 -qtl -up -p</div>
<div>x lapw2 -qtl -dn -p </div>
<div>configure_int_lapw -b total 8 d,dz2,dxy,dx2y2,dxz+dyz</div>
<div>x tetra -up -p</div>
<div>x tetra -dn -p<br>
<br>
</div>
<div>UP (Target was only dyz = 1.0): d: 1.49108, dz2: 0.03198, dxy: 0.04066, dx2y2: 0.09713, dxz+dyz: 1.32129<br>
<br>
DN (Target was dxy, dz2, dxz, dx2-y2 = 1.0 each): d: 3.70166, dz2: 0.72795, dxy: 0.82023, dx2y2: 1.30642, dxz+dyz: 0.84706</div>
<br>
7. Post-processing for Output Density Matrix (lapwdm):<br>
<div>I used a <code>.indmc</code> file same to my <code>.indm</code> and ran:<br>
<div>x lapwdm -up -p</div>
<div>x lapwdm -dn -p</div>
<br>
case.scfdmup (Target was dyz):<br>
<div>irtest 1 8 2.07000000000000</div>
<div> Density matrix UPUP block, real part. L= 2 </div>
<div> 0.08807 0.00000 0.00000 0.00000 0.04017</div>
<div> 0.00000 0.85159 0.00000 0.00000 0.00000</div>
<div> 0.00000 0.00000 0.04101 0.00000 0.00000</div>
<div> 0.00000 0.00000 0.00000 0.85159 0.00000</div>
<div> 0.04017 0.00000 0.00000 0.00000 0.08807</div>
<div>...</div>
<div>:TRA008: TRACE of UPUP MATRIX= 1.92035 0.00000</div>
<br>
case.scfdmdn (Target was dxy, dz2, dxz, dx2-y2):<br>
<div>irtest 1 8 2.07000000000000</div>
<div> Density matrix UPUP block, real part. L= 2 </div>
<div> 0.94475 0.00000 0.00000 0.00000 0.01576</div>
<div> 0.00000 0.48222 0.00000 0.00000 0.00000</div>
<div> 0.00000 0.00000 0.90325 0.00000 0.00000</div>
<div> 0.00000 0.00000 0.00000 0.48222 0.00000</div>
<div> 0.01576 0.00000 0.00000 0.00000 0.94475</div>
<div>...</div>
<div>:TRA008: TRACE of UPUP MATRIX= 3.75719 0.00000</div>
<br>
<br>
Thank you very much for your attention and time!<br>
<br>
Best regards,<br>
Zhiyuan Li</div>
</div>
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