<html><body><div style="color:#000; background-color:#fff; font-family:HelveticaNeue, Helvetica Neue, Helvetica, Arial, Lucida Grande, Sans-Serif;font-size:16px"><div dir="ltr" id="yui_3_16_0_1_1421227471544_4592"><span id="yui_3_16_0_1_1421227471544_5193">Dear Dr. Hill,</span></div><div id="yui_3_16_0_1_1421227471544_4599" dir="ltr"><br><span></span></div><div id="yui_3_16_0_1_1421227471544_4600" dir="ltr"><span id="yui_3_16_0_1_1421227471544_4601">thank you very much for your attention.</span></div><div id="yui_3_16_0_1_1421227471544_4604" dir="ltr"><br><span></span></div><div id="yui_3_16_0_1_1421227471544_4605" dir="ltr"><span id="yui_3_16_0_1_1421227471544_4673">I just tried rotating the MOs [those optimized at the CAS (19,12)] in order to produce the desired active space using:</span></div><div id="yui_3_16_0_1_1421227471544_5529" dir="ltr"><span id="yui_3_16_0_1_1421227471544_4673"><br></span></div><div id="yui_3_16_0_1_1421227471544_4672" dir="ltr"><span style="" class="" id="yui_3_16_0_1_1421227471544_4678"> </span>+++++++++++++++</div><div id="yui_3_16_0_1_1421227471544_4681" dir="ltr"><span id="yui_3_16_0_1_1421227471544_4678"> ROTATE,14.1,16.1,0;<br style="" class=""> ROTATE,6.2,7.2,0;<br style="" class=""> ROTATE,6.3,7.3,0;</span></div><div dir="ltr" id="yui_3_16_0_1_1421227471544_4682">+++++++++++++++</div><div id="yui_3_16_0_1_1421227471544_5641" dir="ltr"><br></div><div id="yui_3_16_0_1_1421227471544_4683" dir="ltr">But, it didn`t help and the re-optimized active space is similar to the initial guess without rotation!</div><div id="yui_3_16_0_1_1421227471544_4934" dir="ltr"><br></div><div id="yui_3_16_0_1_1421227471544_4935" dir="ltr">When I use the MOs optimized at the CAS(9,7) level, which are the desired ones, as initial guess for the subsequent CAS(19,12), it seems that the optimizer converges towards another local minimum, as can be seen from here:</div><div id="yui_3_16_0_1_1421227471544_5581" dir="ltr"><br></div><div id="yui_3_16_0_1_1421227471544_5031" dir="ltr">+++++++++++++++<br></div><div id="yui_3_16_0_1_1421227471544_5026" dir="ltr"> ITER. MIC NCI NEG ENERGY(VAR) ENERGY(PROJ) ENERGY CHANGE GRAD(0) GRAD(ORB) GRAD(CI) STEP TIME<br style="" class=""><br style="" class=""> 1 40 177 0 -6582.87557885 -6582.87558251 -0.00000366 0.00081842 0.00012663 0.00005381 0.18D-01 6.14<br style="" class=""> 2 50 156 0 -6582.87599307 -6582.87895778 -0.00296472 0.00794192 0.00010914 0.02988693 0.91D-01 13.23<br style="" class=""> 3 50 182 0 -6582.88373013 -6582.88385640 -0.00012627 0.01894572 0.00000005 0.00182617 0.99D-02 19.38<br style="" class=""> 4 23 90 0 -6582.88385665 -6582.88385666 0.00000000 0.00004359 0.00000096 0.00001591 0.50D-04 22.57<br style="" class=""><br style="" class=""> ** WVFN **** CONVERGENCE REACHED, FINAL GRADIENT: 0.10D-05</div><div id="yui_3_16_0_1_1421227471544_5078" dir="ltr">+++++++++++++++</div><div id="yui_3_16_0_1_1421227471544_5493" dir="ltr"><br></div><div dir="ltr">The same occurs when rotating the MOs:</div><div id="yui_3_16_0_1_1421227471544_5582" dir="ltr"> <br></div><div id="yui_3_16_0_1_1421227471544_5462" dir="ltr">+++++++++++++++</div><div id="yui_3_16_0_1_1421227471544_5461" dir="ltr"> ITER. MIC NCI NEG ENERGY(VAR) ENERGY(PROJ) ENERGY CHANGE GRAD(0) GRAD(ORB) GRAD(CI) STEP TIME<br style="" class=""><br style="" class=""> 1 10 60 0 -6582.87555809 -6582.87560513 -0.00004704 0.00646904 0.00000020 0.00000008 0.45D+00 4.83<br style="" class=""> 2 13 69 0 -6582.87568695 -6582.87545761 0.00022935 0.00115422 0.00000007 0.00000013 0.85D+00 10.00<br style="" class=""> 3 13 68 0 -6582.87561557 -6582.87551002 0.00010555 0.00090474 0.00000005 0.00000014 0.60D+00 15.06<br style="" class=""> 4 13 69 0 -6582.87561503 -6582.87587317 -0.00025814 0.00055427 0.00000004 0.00000007 0.32D+01 20.08<br style="" class=""> 5 15 52 0 -6582.87931724 -6582.88786934 -0.00855210 0.00561534 0.00000052 0.00000097 0.29D+01 24.34<br style="" class=""> 6 17 59 0 -6582.87701680 -6582.86990141 0.00711539 0.01343667 0.00000039 0.00000009 0.33D+01 29.07<br style="" class=""> 7 12 57 0 -6582.88278094 -6582.88389759 -0.00111665 0.05034000 0.00000131 0.00000071 0.50D+00 33.61<br style="" class=""> 8 10 57 0 -6582.88381208 -6582.88385534 -0.00004326 0.00751312 0.00000015 0.00000007 0.56D-01 38.10<br style="" class=""> 9 10 47 0 -6582.88385651 -6582.88385663 -0.00000013 0.00064537 0.00000001 0.00000011 0.24D-02 42.21<br style="" class=""> 10 9 39 0 -6582.88385665 -6582.88385665 0.00000000 0.00009879 0.00000001 0.00000007 0.14D-03 45.91<br style="" class=""><br style="" class=""> ** WVFN **** CONVERGENCE REACHED, FINAL GRADIENT: 0.26D-04</div><div id="yui_3_16_0_1_1421227471544_5497" dir="ltr">+++++++++++++++</div><div id="yui_3_16_0_1_1421227471544_5142" dir="ltr"><br></div><div id="yui_3_16_0_1_1421227471544_5498" dir="ltr">But I think, according to the state-averaging, orbital and CI gradients of the first iteration etc., the initial guess is good enough and need not be changed as much as it is changed by the optimazer. Is there any way for fettering the freedom of the optimizer?</div><div id="yui_3_16_0_1_1421227471544_5390" dir="ltr"><br></div><div id="yui_3_16_0_1_1421227471544_5389" dir="ltr">Sincerely yours,</div><div id="yui_3_16_0_1_1421227471544_5499" dir="ltr">Davood.<br> </div><div id="yui_3_16_0_1_1421227471544_4684"><br> </div><div id="yui_3_16_0_1_1421227471544_4596" style="font-family: HelveticaNeue, Helvetica Neue, Helvetica, Arial, Lucida Grande, Sans-Serif; font-size: 16px;"> <div id="yui_3_16_0_1_1421227471544_4595" style="font-family: HelveticaNeue, Helvetica Neue, Helvetica, Arial, Lucida Grande, Sans-Serif; font-size: 16px;"> <div id="yui_3_16_0_1_1421227471544_4594" dir="ltr"> <hr id="yui_3_16_0_1_1421227471544_4593" size="1"> <font id="yui_3_16_0_1_1421227471544_4607" size="2" face="Arial"> <b id="yui_3_16_0_1_1421227471544_4933"><span id="yui_3_16_0_1_1421227471544_4932" style="font-weight:bold;">From:</span></b> Grant Hill <grant.hill@sheffield.ac.uk><br> <b><span style="font-weight: bold;">To:</span></b> Davood Alizadeh <alizadeh_davood@yahoo.com> <br><b><span style="font-weight: bold;">Cc:</span></b> "molpro-user@molpro.net" <molpro-user@molpro.net> <br> <b><span style="font-weight: bold;">Sent:</span></b> Wednesday, 14 January 2015, 20:06:32<br> <b><span style="font-weight: bold;">Subject:</span></b> Re: [molpro-user] SACASSCF in MOLPRO & ORCA<br> </font> </div> <div id="yui_3_16_0_1_1421227471544_4608" class="y_msg_container"><br><div id="yui_3_16_0_1_1421227471544_4609" dir="ltr">Dear Davood,<br clear="none"><br clear="none">Have you tried rotating the orbitals to produce the active space you desire?<br clear="none"><br clear="none">See the following manual page: <a id="yui_3_16_0_1_1421227471544_4610" shape="rect" href="http://www.molpro.net/info/2012.1/doc/manual/node240.html" target="_blank">http://www.molpro.net/info/2012.1/doc/manual/node240.html</a><br clear="none"><br clear="none">Best wishes,<br clear="none"><br clear="none">Grant<br clear="none"><br clear="none"><br clear="none"><br clear="none"><div class="qtdSeparateBR"><br><br></div><div class="yqt0444263835" id="yqtfd70264"><br clear="none">> On 13 Jan 2015, at 09:27, Davood Alizadeh <<a shape="rect" ymailto="mailto:alizadeh_davood@yahoo.com" href="mailto:alizadeh_davood@yahoo.com">alizadeh_davood@yahoo.com</a>> wrote:<br clear="none">> <br clear="none">> <br clear="none">> Dear Molpro experts,<br clear="none">> <br clear="none">> Please accept my apologies for my long message. I try to be as concise as possible. <br clear="none">> <br clear="none">> I`m trying to calculate the excitation energies (EEs) of a diatomic molecule (FeAg) using the Molpro and ORCA quantum chemistry packages. What I`m willing to obtain is "identical" excitation energies with these two codes. Despite the slight, at least in my opinion, differences in the SA-CASSCF optimization algorithms implemented in these two codes (e.g.,<br clear="none">> 1) CSF-based optimization of ORCA Vs determinant-based optimization of Molpro in SA-CASSCF calculations<br clear="none">> 2) non-linear coupled optimization of molpro (Werner) Vs uncoupled optimizations (Newton-Rouphson, DIIS, ...) of ORCA<br clear="none">> .<br clear="none">> .<br clear="none">> .)<br clear="none">> <br clear="none">> I`m employing identical basis sets, active spaces, inactive (closed) spaces, etc in these two programs. Thus, I think expecting identical results (either energy deference or absolute energies) might be totally warranted. <br clear="none">> <br clear="none">> The thing is this is the case "just" for a CAS space of (9e,7o) spanned by the atomic {molecular} representations (4s3d^Fe) and (5s^Ag) {sig(3), delta, and pi}, i.e., using this active space, these two codes give identical EEs and absolute energies. However, when the full valence space of (19e,12o), consisting of (4s3d^Fe) and (5s4d^Ag) {sig(4), delta (2), and pi(2)} which is a more adequate/realistic one, is used the Molpro results show considerably different EEs from those of ORCA. I need to confess that these differences which is about 2500 cm^-1 (at the worst case) cannot be considered "huge" but closer results are required for the system at hand.<br clear="none">> <br clear="none">> I think, basically, these discrepancies between EEs of the two codes is due to the following compositions of natural MOs (in irrep A_1) optimized at the CAS(19e,12o) level of theory (from 15.1 to 20.1 is active):<br clear="none">> Orb Occ Energy Coefficients<br clear="none">> ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++<br clear="none">> <br clear="none">> 1 1s 1 1s 1 1s 1 1s 1 1s 1 1s 1 1s 1 1s 1 1s 1 1s <br clear="none">> 1 1s 1 1s 1 1s 1 1s 1 2pz 1 2pz 1 2pz 1 2pz 1 2pz 1 2pz <br clear="none">> 1 2pz 1 2pz 1 2pz 1 2pz 1 3d0 1 3d2+ 1 3d0 1 3d2+ 1 3d0 1 3d2+ <br clear="none">> 1 3d0 1 3d2+ 1 3d0 1 3d2+ 1 4f0 1 4f2+ 1 4f0 1 4f2+ 1 4f0 1 4f2+ <br clear="none">> 1 5g0 1 5g4+ 1 5g2+ 2 1s 2 1s 2 1s 2 1s 2 1s 2 1s 2 1s <br clear="none">> 2 1s 2 1s 2 1s 2 1s 2 1s 2 2pz 2 2pz 2 2pz 2 2pz 2 2pz <br clear="none">> 2 2pz 2 2pz 2 2pz 2 2pz 2 3d0 2 3d2+ 2 3d0 2 3d2+ 2 3d0 2 3d2+ <br clear="none">> 2 3d0 2 3d2+ 2 3d0 2 3d2+ <br clear="none">> 14.1 2.00000 -0.502146 -0.001015 -0.000011 -0.000088 -0.000423 -0.001134 0.000337 0.004706 0.006334 -0.002624 -0.014412<br clear="none">> -0.011738 0.002893 0.090524 -0.033874 0.003529 0.000112 0.000271 -0.002368 -0.007818 -0.001503<br clear="none">> -0.007113 0.037722 0.036990 -0.018287 0.007173 0.000000 0.006388 0.000000 0.000198 0.000000<br clear="none">> 0.024728 0.000000 -0.004631 0.000000 0.000080 0.000000 0.000223 0.000000 0.002026 0.000000<br clear="none">> 0.000075 0.000000 0.000000 -0.000033 -0.000004 -0.000017 0.000296 0.000680 -0.000543 -0.001423<br clear="none">> 0.001182 -0.001467 0.004694 -0.002035 -0.035825 0.000509 0.000045 -0.000310 -0.002299 0.003527<br clear="none">> -0.005320 0.011943 -0.011928 0.043778 -0.253219 0.000000 0.010008 0.000000 0.370894 0.000000<br clear="none">> 0.493947 0.000000 0.310074 0.000000<br clear="none">> <br clear="none">> 15.1 2.00000 -0.498811 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000<br clear="none">> 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000<br clear="none">> 0.000000 0.000000 0.000000 0.000000 0.000000 0.000815 0.000000 -0.000031 0.000000 0.001877<br clear="none">> 0.000000 -0.003179 0.000000 0.013680 0.000000 0.000047 0.000000 -0.000177 0.000000 0.001064<br clear="none">> 0.000000 0.000000 0.000021 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000<br clear="none">> 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000<br clear="none">> 0.000000 0.000000 0.000000 0.000000 0.000000 -0.254068 0.000000 0.010335 0.000000 0.375990<br clear="none">> 0.000000 0.494604 0.000000 0.320878<br clear="none">> <br clear="none">> 16.1 1.99873 -2.707087 -0.000010 0.000000 -0.000001 -0.000009 -0.000011 -0.000013 0.000187 0.000148 0.000024 -0.001313<br clear="none">> 0.000525 -0.000108 0.001382 0.000143 0.325725 0.004979 0.020291 -0.245961 -0.476994 -0.390804<br clear="none">> -0.094062 0.000806 -0.001811 0.000502 0.000440 0.000000 0.000508 0.000000 -0.000169 0.000000<br clear="none">> 0.000107 0.000000 0.000089 0.000000 0.000020 0.000000 0.000058 0.000000 -0.000115 0.000000<br clear="none">> -0.000008 0.000000 0.000000 -0.000048 -0.000007 -0.000019 0.000164 0.000127 0.000039 -0.000312<br clear="none">> -0.000632 0.000584 0.000997 -0.000840 -0.001190 -0.000553 -0.000036 0.000598 0.001010 0.000225<br clear="none">> -0.001080 -0.002101 -0.000195 0.000712 -0.001950 0.000000 0.000078 0.000000 0.002893 0.000000<br clear="none">> 0.003809 0.000000 0.002121 0.000000<br clear="none">> ...<br clear="none">> +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++<br clear="none">> These compositions show that the optimized reference space is spanned by 15.1 (4d^Ag), 16.1 (2p^Fe) ... and the 14.1(4d^Ag) is turned out to be a core orbital whereas it is expected to have this orbital in the active space! The same happens for B_1 and B_2 irreps. <br clear="none">> <br clear="none">> This is my input by the way:<br clear="none">> <br clear="none">> <br clear="none">> <br clear="none">> +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++<br clear="none">> SET,DKROLL=1<br clear="none">> <br clear="none">> {rhf<br clear="none">> wf,73,4,5;<br clear="none">> occ,20,8,8,3;<br clear="none">> closed,17,7,7,2<br clear="none">> orbital,2100.2<br clear="none">> }<br clear="none">> <br clear="none">> {casscf;occ,20,8,8,3;closed,16,7,7,2<br clear="none">> { ITERATIONS;<br clear="none">> DO,internal,2,TO,20;<br clear="none">> }<br clear="none">> start,2100.2;<br clear="none">> WF,73,1,3;state,3<br clear="none">> WF,73,2,3;state,3<br clear="none">> WF,73,3,3;state,3<br clear="none">> WF,73,4,3;state,3<br clear="none">> WF,73,1,5;state,3<br clear="none">> WF,73,2,5;state,3<br clear="none">> WF,73,3,5;state,3<br clear="none">> WF,73,4,5;state,3<br clear="none">> expec2,lxx,lyy,lzz;<br clear="none">> natorb,ci,print;<br clear="none">> ORBITAL,2140.2;<br clear="none">> }<br clear="none">> <br clear="none">> {casscf;occ,20,8,8,3;closed,14,6,6,1<br clear="none">> { ITERATIONS;<br clear="none">> DO,internal,2,TO,20;<br clear="none">> }<br clear="none">> start,2140.2;<br clear="none">> WF,73,1,3;state,3<br clear="none">> WF,73,2,3;state,3<br clear="none">> WF,73,3,3;state,3<br clear="none">> WF,73,4,3;state,3<br clear="none">> WF,73,1,5;state,3<br clear="none">> WF,73,2,5;state,3<br clear="none">> WF,73,3,5;state,3<br clear="none">> WF,73,4,5;state,3<br clear="none">> expec2,lxx,lyy,lzz;<br clear="none">> natorb,ci,print;<br clear="none">> ORBITAL,2140.2;<br clear="none">> }<br clear="none">> +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++<br clear="none">> <br clear="none">> <br clear="none">> Could someone help me about this problem please?<br clear="none">> <br clear="none">> <br clear="none">> <br clear="none">> <br clear="none">> Thanks a lot in advance,<br clear="none">> sincerely yours.<br clear="none">> Davood. </div><br clear="none">> <br clear="none">> <br clear="none">> <br clear="none">> _______________________________________________<br clear="none">> Molpro-user mailing list<br clear="none">> <a shape="rect" ymailto="mailto:Molpro-user@molpro.net" href="mailto:Molpro-user@molpro.net">Molpro-user@molpro.net</a><br clear="none">> <a shape="rect" href="http://www.molpro.net/mailman/listinfo/molpro-user" target="_blank">http://www.molpro.net/mailman/listinfo/molpro-user</a><div class="yqt0444263835" id="yqtfd55466"><br clear="none"></div></div><br><br></div> </div> </div> </div></body></html>