<html><body><div style="color:#000; background-color:#fff; font-family:garamond, new york, times, serif;font-size:12pt"><div><span>Dear Mr. Jose,<br></span></div><div style="color: rgb(0, 0, 0); font-size: 16px; font-family: "Garamond"; background-color: transparent; font-style: normal;"><span><br></span></div><div style="color: rgb(0, 0, 0); font-size: 16px; font-family: "Garamond"; background-color: transparent; font-style: normal;"><span>Thanks for your detail explanation. I'll try to use hybrid function as you suggest. I'll update the results asap.<br></span></div><div style="color: rgb(0, 0, 0); font-size: 16px; font-family: "Garamond"; background-color: transparent; font-style: normal;"><span><br></span></div><div style="color: rgb(0, 0, 0); font-size: 16px; font-family: "Garamond"; background-color: transparent; font-style: normal;"><span>Sincerely yours,<br></span></div><div style="color: rgb(0, 0, 0);
 font-size: 16px; font-family: "Garamond"; background-color: transparent; font-style: normal;"><span><br></span></div><div style="color: rgb(0, 0, 0); font-size: 16px; font-family: "Garamond"; background-color: transparent; font-style: normal;"><span>Iwan D.<br></span></div><div> </div><div style="color:rgb(0, 0, 0);font-size:13px;background-color:transparent;font-style:normal;"><span><font face="lucida console, sans-serif"><font size="2"><b>***<br></b></font></font></span></div><div style="color:rgb(0, 0, 0);font-size:13px;background-color:transparent;font-style:normal;"><span><font face="lucida console, sans-serif"><font size="2"><b>Iwan Darmadi</b></font></font></span><br><span><font face="lucida console, sans-serif"> Undergrad.Student - Department of Physics</font></span><font face="lucida console, sans-serif"><br></font></div><div style="color:rgb(0, 0,
 0);font-size:13px;background-color:transparent;font-style:normal;"><span><font face="lucida console, sans-serif"> Universitas Indonesia</font></span></div><div style="color:rgb(0, 0, 0);font-size:13px;background-color:transparent;font-style:normal;" class="yui_3_2_0_2_1344683897969181"><a rel="nofollow" target="_blank" href="http://www.iwandarmadi.wordpress.com/"><b></b></a><br></div>  <div style="font-size: 12pt; font-family: "garamond", "new york", "times", serif;"> <div style="font-size: 12pt; font-family: "times new roman", "new york", "times", serif;"> <div dir="ltr"> <font size="2" face="Arial"> <hr size="1">  <b><span style="font-weight:bold;">From:</span></b> ""José C. Conesa"" <jcconesa@icp.csic.es><br> <b><span style="font-weight: bold;">To:</span></b> Iwan Darmadi <iwan_darmadi@rocketmail.com> <br><b><span style="font-weight: bold;">Cc:</span></b> PWSCF Forum
 <pw_forum@pwscf.org> <br> <b><span style="font-weight: bold;">Sent:</span></b> Friday, January 25, 2013 6:31 PM<br> <b><span style="font-weight: bold;">Subject:</span></b> Re: [Pw_forum] Fail to predict semiconductor<br> </font> </div> <br>
<div id="yiv1185301972">
  

    
  
  <div>
    Dear Iwan,<br>
    In the paper you quote, the Ti:ZnO case has the Ti levels inside the
    ZnO conduction band (see fig. 2) - and this even though the latter
    band has been pushed up by applying an ad hoc shift to the Zn 4s
    levels, so that the correct gap of ZnO is obtained. Thus it does not
    seem that the calculation reported there predicts this system to be
    a semiconductor. Of course, experimentally it may happen that the
    material prepared, especially if it was made in even mildly
    oxidizing environment, contains cation vacancies, possibly located
    close to the Ti atoms (assuming these to be at tetrahedral sites -
    which is not a preferred coordination for Ti) so that it could
    behave as semiconductor.<br>
    In any case computing correctly band gaps and level positions in
    these systems is tricky even with post-DFT treatments. I try to
    avoid if possible DFT+U (treating differently different electrons is
    not very elegant), and to use hybrids instead. One problem with the
    latter is that the fraction of Fock exchange to be used can be
    questioned. Indeed one same fraction is not valid for both TiO2 and
    ZnO. You can approach the situation better if that fraction is tuned
    to the dielectric constant of the material. If you are interested in
    this specific issue I invite you to look at my recent papers
    
    <span style="font-size:11.0pt;
" lang="EN-US">J. Phys. </span><span style="font-size:11.0pt;

">Chem. C</span><span style="font-size:11.0pt;
"> 116 (2012) 18884</span>
    
    
    

    
    

    

    
    
    <style>
<!--
#yiv1185301972  
 _filtered #yiv1185301972 {font-family:Courier;panose-1:2 7 4 9 2 2 5 2 4 4;}
 _filtered #yiv1185301972 {font-family:Courier;panose-1:2 7 4 9 2 2 5 2 4 4;}
 _filtered #yiv1185301972 {panose-1:0 0 0 0 0 0 0 0 0 0;}
 _filtered #yiv1185301972 {panose-1:0 0 0 0 0 0 0 0 0 0;}
#yiv1185301972  
#yiv1185301972 p.yiv1185301972MsoNormal, #yiv1185301972 li.yiv1185301972MsoNormal, #yiv1185301972 div.yiv1185301972MsoNormal
        {margin:0cm;margin-bottom:.0001pt;font-size:12.0pt;font-family:Courier;}
#yiv1185301972 .yiv1185301972MsoChpDefault
        {font-size:10.0pt;}
 _filtered #yiv1185301972 {margin:70.85pt 3.0cm 70.85pt 3.0cm;}
#yiv1185301972 div.yiv1185301972WordSection1
        {}
-->
</style>
    
    
    
    

    
    

    

    
    and Catal. Today in press (doi: 
    
    <span style="font-size:11.0pt;

color:black;" lang="EN-US">10.1016/j.cattod.2012.08.039)</span>
    
    
    

    
    

    

    
    
    <style>
<!--
#yiv1185301972  
 _filtered #yiv1185301972 {font-family:Courier;panose-1:2 7 4 9 2 2 5 2 4 4;}
 _filtered #yiv1185301972 {font-family:Courier;panose-1:2 7 4 9 2 2 5 2 4 4;}
#yiv1185301972  
#yiv1185301972 p.yiv1185301972MsoNormal, #yiv1185301972 li.yiv1185301972MsoNormal, #yiv1185301972 div.yiv1185301972MsoNormal
        {margin:0cm;margin-bottom:.0001pt;font-size:12.0pt;font-family:Courier;}
#yiv1185301972 .yiv1185301972MsoChpDefault
        {font-size:10.0pt;}
 _filtered #yiv1185301972 {margin:70.85pt 3.0cm 70.85pt 3.0cm;}
#yiv1185301972 div.yiv1185301972WordSection1
        {}
-->
</style> where this solution is explained better, although its
    suitability for possibly metallic systems like yours can be
    questioned as well.<br>
    Regards,<br>
    José-Carlos<br>
    <br>
    
    <style>
<!--
#yiv1185301972  
 _filtered #yiv1185301972 {font-family:Courier;panose-1:2 7 4 9 2 2 5 2 4 4;}
 _filtered #yiv1185301972 {font-family:Courier;panose-1:2 7 4 9 2 2 5 2 4 4;}
 _filtered #yiv1185301972 {panose-1:0 0 0 0 0 0 0 0 0 0;}
 _filtered #yiv1185301972 {panose-1:0 0 0 0 0 0 0 0 0 0;}
#yiv1185301972  
#yiv1185301972 p.yiv1185301972MsoNormal, #yiv1185301972 li.yiv1185301972MsoNormal, #yiv1185301972 div.yiv1185301972MsoNormal
        {margin:0cm;margin-bottom:.0001pt;font-size:12.0pt;font-family:Courier;}
#yiv1185301972 .yiv1185301972MsoChpDefault
        {font-size:10.0pt;}
 _filtered #yiv1185301972 {margin:70.85pt 3.0cm 70.85pt 3.0cm;}
#yiv1185301972 div.yiv1185301972WordSection1
        {}
-->
</style>
    <div class="yiv1185301972moz-cite-prefix">El 23/01/2013 15:56, Iwan Darmadi
      escribió:<br>
    </div>
    <blockquote type="cite">
      <div style="color: rgb(0, 0, 0); background-color: rgb(255, 255, 255); font-size: 12pt; font-family: "garamond", "new york", "times", serif;">
        <div id="yiv1185301972">
          <div>
            <div style="color:rgb(0, 0, 0);background-color:rgb(255,
              255, 255);font-size:12pt;

">
              <div id="yiv1185301972">
                <div>
                  <div style="color:rgb(0, 0, 0);
background-color:rgb(255, 255, 255);font-size:12pt;

" class="yiv1185301972yui_3_7_2_15_1358952486394_49">
                    <div id="yiv1185301972yui_3_7_2_16_1358929912581_49"> Dear
                      Mr.Jose,</div>
                    <div><br>
                    </div>
                    <div id="yiv1185301972yui_3_7_2_16_1358929912581_122">Yes,
                      I do. But, as far as I know, transition metal
                      doped zno is semiconductor even theoretically
                      (according for example PRB 79/165202 and ). So I
                      assumed that without cation vacancy, Ti doped ZnO
                      might be semiconductor also.</div>
                    <div><br>
                    </div>
                    <div>Regards,</div>
                    <div>ID</div>
                    <div style="color:rgb(0, 0,
                      0);font-size:13px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_16_1358929912581_53"><span><font face="lucida console, sans-serif"><font size="2"><b>***<br>
                            </b></font></font></span></div>
                    <div style="color:rgb(0, 0,
                      0);font-size:13px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_16_1358929912581_55"><span><font face="lucida console, sans-serif"><font size="2"><b>Iwan Darmadi</b></font></font></span><br>
                      <span><font face="lucida console, sans-serif"> Undergrad.Student
                          - Department of Physics</font></span><font face="lucida console, sans-serif"><br>
                      </font></div>
                    <div style="color:rgb(0, 0,
                      0);font-size:13px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_16_1358929912581_57"><span><font face="lucida console, sans-serif"> Universitas
                          Indonesia</font></span></div>
                    <div style="color:rgb(0, 0,
                      0);font-size:13px;background-color:transparent;font-style:normal;" class="yiv1185301972yui_3_2_0_2_1344683897969181" id="yiv1185301972yui_3_7_2_16_1358929912581_59"><br id="yiv1185301972yui_3_7_2_16_1358929912581_61">
                    </div>
                    <div style="font-size: 12pt; font-family: "garamond", "new york", "times", serif;" id="yiv1185301972yui_3_7_2_16_1358929912581_64" class="yiv1185301972yui_3_7_2_16_1358929912581_63
                      yiv1185301972yui_3_7_2_15_1358952486394_59">
                      <div style="font-size:12pt;

" class="yiv1185301972yui_3_7_2_16_1358929912581_72
                        yiv1185301972yui_3_7_2_15_1358952486394_60">
                        <div dir="ltr"> <font face="Arial" size="2">
                            <hr size="1"> <b><span style="font-weight:bold;" id="yiv1185301972yui_3_7_2_16_1358929912581_116">From:</span></b>
                            Jose C. Conesa <a rel="nofollow" class="yiv1185301972moz-txt-link-rfc2396E" ymailto="mailto:jcconesa@icp.csic.es" target="_blank" href="mailto:jcconesa@icp.csic.es"><jcconesa@icp.csic.es></a><br>
                            <b><span style="font-weight:bold;">To:</span></b>
                            Iwan Darmadi
                            <a rel="nofollow" class="yiv1185301972moz-txt-link-rfc2396E" ymailto="mailto:iwan_darmadi@rocketmail.com" target="_blank" href="mailto:iwan_darmadi@rocketmail.com"><iwan_darmadi@rocketmail.com></a>; PWSCF
                            Forum <a rel="nofollow" class="yiv1185301972moz-txt-link-rfc2396E" ymailto="mailto:pw_forum@pwscf.org" target="_blank" href="mailto:pw_forum@pwscf.org"><pw_forum@pwscf.org></a> <br>
                            <b><span style="font-weight:bold;">Sent:</span></b>
                            Wednesday, January 23, 2013 3:09 PM<br>
                            <b><span style="font-weight:bold;">Subject:</span></b>
                            Re: [Pw_forum] Fail to predict semiconductor<br>
                          </font> </div>
                        <br>
                        <div id="yiv1185301972">
                          <div>
                            <div class="yiv1185301972moz-cite-prefix">Dear
                              Iwan,<br>
                              Do you know whether the experimentally
                              known Ti doped ZnO contains cation
                              vacancies?<br>
                              Good luck,<br>
                              José Carlos<br>
                              <br>
                              El 23/01/2013 6:50, Iwan Darmadi escribió:<br>
                            </div>
                            <blockquote type="cite">
                              <div style="color:rgb(0, 0, 0);background-color:rgb(255, 255, 255);font-size:12pt;

" class="yiv1185301972yui_3_7_2_16_1358929912581_78
yiv1185301972yui_3_7_2_15_1358952486394_66">
                                <div id="yiv1185301972">
                                  <div>
                                    <div style="color:rgb(0, 0,
                                      0);background-color:rgb(255, 255,
                                      255);font-size:12pt;">
                                      <div id="yiv1185301972yui_3_7_2_15_1358917927192_49"><span id="yiv1185301972yui_3_7_2_15_1358917927192_73">Dear all,<br>
                                        </span></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:16px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_88"><span id="yiv1185301972yui_3_7_2_15_1358917927192_90"><br id="yiv1185301972yui_3_7_2_15_1358917927192_92">
                                        </span></div>
                                      <div id="yiv1185301972yui_3_7_2_15_1358917927192_83" style="color:rgb(0, 0,
                                        0);font-size:16px;background-color:transparent;font-style:normal;"><span id="yiv1185301972yui_3_7_2_15_1358917927192_81">I have calculated
                                          electronic structure of Ti
                                          doped ZnO in both GGA and
                                          GGA+U scheme. Both scheme
                                          predicts Ti doped ZnO is
                                          metallic. In contrary, Ti
                                          doped ZnO is well known as
                                          semiconductor experimentally.
                                          At first glance, I thought it
                                          was local minimum problem of
                                          DFT+U (like FeO problem in Mr.
                                          Himmetoglu's tutorial). Then I
                                          try to copy Mr. Himmetoglu's
                                          trick to override a
                                          "suspected" fully occupied
                                          orbitals of Ti. Sadly, nothing
                                          change,  it's still a
                                          metallic.</span><span id="yiv1185301972yui_3_7_2_15_1358917927192_112"><br id="yiv1185301972yui_3_7_2_15_1358917927192_121">
                                        </span></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:16px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_125"><span id="yiv1185301972yui_3_7_2_15_1358917927192_127"><br id="yiv1185301972yui_3_7_2_15_1358917927192_129">
                                        </span></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:16px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_119"><span id="yiv1185301972yui_3_7_2_15_1358917927192_117">Now,
                                          I am confused whether this is
                                          a really local minimum problem
                                          or intrinsic limitation of DFT
                                          it self.</span><span id="yiv1185301972yui_3_7_2_15_1358917927192_146"><br id="yiv1185301972yui_3_7_2_15_1358917927192_163">
                                        </span></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:16px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_167"><span id="yiv1185301972yui_3_7_2_15_1358917927192_169"><br id="yiv1185301972yui_3_7_2_15_1358917927192_171">
                                        </span></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:16px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_161"><span id="yiv1185301972yui_3_7_2_15_1358917927192_159">Do

                                          anyone here have suggestions
                                          so I can get semiconductor Ti
                                          doped ZnO in the calculation ?<br>
                                        </span></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:16px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_140"><span id="yiv1185301972yui_3_7_2_15_1358917927192_142"><br id="yiv1185301972yui_3_7_2_15_1358917927192_144">
                                        </span></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:16px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_134"><span id="yiv1185301972yui_3_7_2_15_1358917927192_98">Ps.<br id="yiv1185301972yui_3_7_2_15_1358917927192_182">
                                        </span></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:16px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_180"><span id="yiv1185301972yui_3_7_2_15_1358917927192_178">I
                                          have also attached my input
                                          and output file.<br>
                                        </span></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:13px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_53"><span><font face="lucida
                                            console, sans-serif"><font size="2"><b>***<br>
                                              </b></font></font></span></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:13px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_55"><span><font face="lucida
                                            console, sans-serif"><font size="2"><b>Iwan Darmadi</b></font></font></span><br>
                                        <span><font face="lucida
                                            console, sans-serif"> Undergrad.Student

                                            - Department of Physics</font></span><font face="lucida console,
                                          sans-serif"><br>
                                        </font></div>
                                      <div style="color:rgb(0, 0,
                                        0);font-size:13px;background-color:transparent;font-style:normal;" id="yiv1185301972yui_3_7_2_15_1358917927192_57"><span><font face="lucida
                                            console, sans-serif"> Universitas

                                            Indonesia</font></span><span class="yiv1185301972yui_3_2_0_2_1344683897969186" id="yiv1185301972yui_3_7_2_15_1358917927192_78"><br>
                                        </span></div>
                                    </div>
                                  </div>
                                </div>
                              </div>
                              <br>
                              <br>
                              <pre>_______________________________________________
Pw_forum mailing list
<a rel="nofollow" class="yiv1185301972moz-txt-link-abbreviated" ymailto="mailto:Pw_forum@pwscf.org" target="_blank" href="mailto:Pw_forum@pwscf.org">Pw_forum@pwscf.org</a>
http://pwscf.org/mailman/listinfo/pw_forum</pre>
                            </blockquote>
                            <br>
                            <br>
                            <pre class="yiv1185301972moz-signature">-- 
José C. Conesa
Instituto de Catálisis y Petroleoquímica, CSIC
Marie Curie 2, Cantoblanco
28049 Madrid - Spain
Tel. +34-915854766</pre>
                          </div>
                        </div>
                        <br>
                        <br>
                      </div>
                    </div>
                  </div>
                </div>
              </div>
            </div>
          </div>
        </div>
      </div>
    </blockquote>
    <br>
    <pre class="yiv1185301972moz-signature">-- 
José C. Conesa
Instituto de Catálisis y Petroleoquímica, CSIC
Marie Curie 2, Cantoblanco
28049 Madrid - Spain
Tel. +34-915854766
</pre>
  </div>

</div><br><br> </div> </div>  </div></body></html>