<meta http-equiv="Content-Type" content="text/html; charset=utf-8"><div dir="ltr">To clarify one point, you have to be careful about the meaning of Co"4+". <div><br></div><div>The "4+" is a formal valence, which is quite well reproduced by the bond-valence sums (BVS), e.g. do "x nn ; grep Bond *tnn". It is also what people use when they refer to different atom states as observed by XPS, EELS etc.</div><div><br></div><div>This is different from the actual charge within the muffin tins (look at the relevant :CTO), the d-electron density from the density matrix, the spin from the magnetic moment, the Bader charge and the dynamic polarization charge (Born charge).<br></div></div><div class="gmail_extra"><br><div class="gmail_quote">On Tue, May 10, 2016 at 7:33 AM, Peter Blaha <span dir="ltr"><<a href="mailto:pblaha@theochem.tuwien.ac.at" target="_blank">pblaha@theochem.tuwien.ac.at</a>></span> wrote:<br><blockquote class="gmail_quote" style="margin:0 0 0 .8ex;border-left:1px #ccc solid;padding-left:1ex">a) I don't think that you will ever get a 3d-occupation which is in<br>
agreement with the "formal" valence (therfore this is called "formal").<br>
This starts even for a very ionic TiO2, where formally the 3d electrons<br>
of Ti4+ should all be empty, but are not in reality.<br>
<br>
b) Try to stabilize a "high-spin" state for Co by changing the 0.8 on<br>
spin-dn to 0.2, and the 0.59 to 0.9 in spin-up.<br>
After modification of the dmatup/dn files, run:<br>
<br>
x orb -up/dn<br>
runsp -orbc<br>
save constraint_high_spin<br>
runsp -orb<br>
<br>
and check the final results, if the spin (charge) state has changed.<br>
Also compare the total energies of the present and the new solution.<br>
<div><div class="h5"><br>
<br>
On 05/10/2016 01:54 PM, Komal Bapna wrote:<br>
> Dear Prof. Peter<br>
> Thank you for your kind reply..<br>
><br>
> The Density matrix for Co up spin is..<br>
> 0.84607 0.00000 0.00000 0.00000 -0.08661<br>
> 0.00000 0.92206 0.00000 0.00000 0.00000<br>
> 0.00000 0.00000 0.59673 0.00000 0.00000<br>
> 0.00000 0.00000 0.00000 0.92206 0.00000<br>
> -0.08661 0.00000 0.00000 0.00000 0.84607<br>
> Total electrons: 4.13298<br>
> and Density matrix for Co dn spin is:<br>
> 0.20583 0.00000 0.00000 0.00000 0.06263<br>
> 0.00000 0.80064 0.00000 0.00000 0.00000<br>
> 0.00000 0.00000 0.25923 0.00000 0.00000<br>
> 0.00000 0.00000 0.00000 0.80064 0.00000<br>
> 0.06263 0.00000 0.00000 0.00000 0.20583<br>
> Total electrons: 2.27217<br>
><br>
> This gives me the net spin moment of 1.86 muB on Co.<br>
> I understood by changing the occupancies we can change the spin state.<br>
> Still I am confused whether I can use these occupation numbers of<br>
> electrons in the respective orbitals to find the spin state of Co.Here,<br>
> total number of electrons is 6.4, 1.4 electrons higher than the expected<br>
> value for Co4+ ion. I may consider the extra electrons due to the<br>
> bonding of Co-O bonds. But, I am really unable to calculate the spin<br>
> state from the present configuration. Please suggest how to calculate<br>
> spin state for the given configuration, so that I can modify further.<br>
><br>
> Thanks and Regards<br>
><br>
> On Mon, May 9, 2016 at 3:59 PM, Komal Bapna <<a href="mailto:komal.bapna@gmail.com">komal.bapna@gmail.com</a><br>
</div></div><span class="">> <mailto:<a href="mailto:komal.bapna@gmail.com">komal.bapna@gmail.com</a>>> wrote:<br>
><br>
> Sir,<br>
><br>
> Its true that we can not generate "ionic" electron density with lstart/dstart. When I tried to modify .inst file according to the Co4+ ionic state, it showed error.<br>
><br>
> My query is that how can we generate spin state configuration for such an ionic state, it spin states for Co and Co4+ are different and accordingly the magnetic moments.<br>
><br>
><br>
> Please suggest.<br>
><br>
><br>
> Thanks<br>
><br>
><br>
> On Fri, May 6, 2016 at 3:18 PM, Komal Bapna <<a href="mailto:komal.bapna@gmail.com">komal.bapna@gmail.com</a><br>
</span><div><div class="h5">> <mailto:<a href="mailto:komal.bapna@gmail.com">komal.bapna@gmail.com</a>>> wrote:<br>
><br>
> Dear Wien users<br>
><br>
> I am working on Sr2CoO4. Here I wanted to study the system with different spin state configuration of Co4+, which is known to be valence state of Co in this system. I could understand how to create:<br>
> (a) High-spin configuration<br>
> (b) Intermediate spin configuration<br>
> (c) Low-spin configuration<br>
> for the given Co atoms in the .inst file as<br>
><br>
> Co<br>
> Ar 3<br>
> 3, 2,2.0 N<br>
> 3, 2,2.0 N<br>
> 3,-3,3.0 N<br>
> 3,-3,0.0 N<br>
> 4,-1,1.0 N<br>
> 4,-1,1.0 N (for HS state)<br>
> and<br>
> Co<br>
> Ar 3<br>
> 3, 2,2.0 N<br>
> 3, 2,2.0 N<br>
> 3,-3,2.0 N<br>
> 3,-3,1.0 N<br>
> 4,-1,1.0 N<br>
> 4,-1,1.0 N (for IS state)<br>
><br>
><br>
> But my query is that .inst file takes Co as neutral atom (9<br>
> electrons:3d74s2) and accordingly its spin state. As if Co were in 4+ state, I would have 5 electrons in 3d state (3d54s0) rather 9 electrons as is revealed from .inst file now.<br>
><br>
> Please suggest me how to give spin state for Co4+ for this system.<br>
><br>
><br>
> Thanks<br>
><br>
><br>
><br>
> --<br>
</div></div>> *Komal*<br>
><br>
><br>
><br>
><br>
> --<br>
> *Komal*<br>
><br>
><br>
><br>
><br>
> --<br>
> *Komal*<br>
><br>
><br>
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><br>
<br>
--<br>
<br>
P.Blaha<br>
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</blockquote></div><br><br clear="all"><div><br></div>-- <br><div class="gmail_signature"><div dir="ltr"><div><div dir="ltr"><div><div dir="ltr"><div dir="ltr"><div dir="ltr"><div dir="ltr"><div dir="ltr"><span style="font-size:12.8px">Professor Laurence Marks</span><br></div><div dir="ltr"><span style="font-size:12.8px">"Research is to see what everybody else has seen, and to think what nobody else has thought", </span><span style="font-size:12.8px">Albert Szent-Gyorgi</span><br><a href="http://www.numis.northwestern.edu" target="_blank">www.numis.northwestern.edu</a> ; <span style="font-size:12.8px">Corrosion in 4D: </span><a href="http://MURI4D.numis.northwestern.edu" style="font-size:12.8px" target="_blank">MURI4D.numis.northwestern.edu</a><div><span style="font-size:12.8px">Partner of the CFW 100% program for gender equity, </span><a href="http://www.cfw.org/100-percent" style="font-size:12.8px" target="_blank">www.cfw.org/100-percent</a></div><div>Co-Editor, Acta Cryst A</div></div></div></div></div></div></div></div></div></div></div>
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