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<p class="MsoNormal">Hi,<o:p></o:p></p>
<p class="MsoNormal"><o:p> </o:p></p>
<p class="MsoNormal">When calculating a vertical excitation energy using MRCI-F12, we found one molecule (CrCl) for which we get alarmingly different results when the preceding CASSCF is run with the doubly-occupied orbitals “frozen” or merely “closed.” Here
is the input file:<o:p></o:p></p>
<div style="mso-element:para-border-div;border:none;border-bottom:double windowtext 2.25pt;padding:0in 0in 1.0pt 0in">
<p class="MsoNormal" style="border:none;padding:0in"><o:p> </o:p></p>
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<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">***, CrCl, illustrating mysterious inconsistency in core/valence MRCI partitioning (6A1 state and 8B1 state)<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">MEMORY,100,M<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">angstrom<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">geometry={<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Cr;<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Cl,1,r;<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">}<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">r=2.20219779<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">basis={<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">default,AWCVTZ<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">set,jk<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">default,def2-QZVPP/JKFIT<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">set,df<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">default,aug-cc-pwCVTZ/MP2FIT<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">s,Cr,1125.39,341.170,73.9951,31.2459,18.9340,9.25672,6.42575,3.38099,1.74898,0.984534,0.758085,0.337239,0.128563,0.075795,0.042102<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">p,Cr,421.364,189.344,39.4212,18.5562,9.17740,7.23806,3.89384,1.91685,1.28017,0.662766,0.331280,0.151677,0.073572,0.057624<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">d,Cr,161.521,50.5342,22.2636,9.60004,6.76492,4.13610,2.11763,1.20327,0.710380,0.315499,0.126834,0.064490<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">f,Cr,80.4841,30.8651,10.8536,5.83615,3.98155,2.21072,1.13224,0.589006,0.283022,0.162113,0.132695<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">g,Cr,31.5558,13.1525,6.19049,4.29099,2.33217,1.19468,0.492783,0.203392,0.640652<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">h,Cr,14.3240,6.43119,3.90826,2.30624,0.920789,0.385634<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">i,Cr,8.00125,4.77640,2.17128,0.883034<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">}<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">! sextet state (6S, 6A1)<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">{rhf<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""> wf,sym=1,spin=5;<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">}<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">! CASSCF(21/14)<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">{multi<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""> occ,13,5,5,1;<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""> closed,6,2,2,0;<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">! frozen,6,2,2,0;<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">}<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">! MRCI
<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">{mrci-f12,df_basis=df,df_basis_exch=jk,ri_basis=df<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""> core,6,2,2,0<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">}<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">gs=energd<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">! octet 8B1<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">{rhf<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""> wf,sym=2,spin=7<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">}<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">{multi<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""> occ,13,5,5,1;<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""> closed,6,2,2,0;<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">! frozen,6,2,2,0;<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">}<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">! MRCI
<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">{mrci-f12,df_basis=df,df_basis_exch=jk,ri_basis=df<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""> core,6,2,2,0<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">}<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">xs=energd<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<div style="mso-element:para-border-div;border:none;border-bottom:double windowtext 2.25pt;padding:0in 0in 1.0pt 0in">
<p class="MsoNormal" style="border:none;padding:0in"><span style="font-size:8.0pt;font-family:"Courier New"">excitation_energy=(xs-gs)*TOEV<o:p></o:p></span></p>
</div>
<p class="MsoNormal"><o:p> </o:p></p>
<p class="MsoNormal">The corresponding output file yields EXCITATION_ENERGY = 3.30659542 EV.<o:p></o:p></p>
<p class="MsoNormal">But if the two “frozen” lines are uncommented, the final result is EXCITATION_ENERGY = 4.18284549 EV.<o:p></o:p></p>
<p class="MsoNormal"><o:p> </o:p></p>
<p class="MsoNormal">The biggest difference I see in the output files is the section of the MRCI describing the core/valence energies. In the first job, this section for the two MRCI calculations (lower and upper states) is:<o:p></o:p></p>
<p class="MsoNormal"><o:p> </o:p></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Nuclear energy: 98.04037687<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Core energy: -1476.38524047<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Zeroth-order valence energy: -25.75585178<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Zeroth-order total energy: -1404.10071539<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">First-order energy: -98.88176684<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Nuclear energy: 98.04037687<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Core energy: -1476.38451622<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Zeroth-order valence energy: -23.65850589<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Zeroth-order total energy: -1402.00264524<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">First-order energy: -100.79974424<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<p class="MsoNormal">But in the second case (with the doubly-occupied orbitals optimized during the CASSCF) I get:<o:p></o:p></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Nuclear energy: 98.04037687<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Core energy: -1409.15674314<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Zeroth-order valence energy: -68.87794571<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Zeroth-order total energy: -1379.99431197<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">First-order energy: -122.98962991<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New""><o:p> </o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Nuclear energy: 98.04037687<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Core energy: -1476.23082148<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Zeroth-order valence energy: -24.00693777<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">Zeroth-order total energy: -1402.19738238<o:p></o:p></span></p>
<p class="MsoNormal"><span style="font-size:8.0pt;font-family:"Courier New"">First-order energy: -100.60555506<o:p></o:p></span></p>
<p class="MsoNormal"><o:p> </o:p></p>
<p class="MsoNormal">In the second job, about 67 hartree has been moved from the core, but only for the lower state. I spent a couple of hours thrashing keywords but have had no luck understanding or solving this problem. I did try following the CASSCF by
another CASSCF with the optimized orbitals “frozen”, but that made no difference. I tried setting the PRCORE array but couldn’t obtain any effect.
<o:p></o:p></p>
<p class="MsoNormal"><o:p> </o:p></p>
<p class="MsoNormal">Grateful for any help or insight,<o:p></o:p></p>
<p class="MsoNormal">Karl<o:p></o:p></p>
<p class="MsoNormal"><o:p> </o:p></p>
<p class="MsoNormal"><o:p> </o:p></p>
<p class="MsoNormal"><span style="font-size:10.0pt;font-family:"Arial","sans-serif"">-------------------------------------------------------------------</span><o:p></o:p></p>
<p class="MsoNormal"><span style="font-size:10.0pt;font-family:"Arial","sans-serif"">Dr. Karl K. Irikura</span><o:p></o:p></p>
<p class="MsoNormal"><span style="font-size:10.0pt;font-family:"Arial","sans-serif"">National Institute of Standards and Technology</span><o:p></o:p></p>
<p class="MsoNormal"><span style="font-size:10.0pt;font-family:"Arial","sans-serif"">100 Bureau Drive, mail stop 8320</span><o:p></o:p></p>
<p class="MsoNormal"><span style="font-size:10.0pt;font-family:"Arial","sans-serif"">Gaithersburg, MD 20899-8320</span><o:p></o:p></p>
<p class="MsoNormal"><span style="font-size:10.0pt;font-family:"Arial","sans-serif"">voice: 301-975-2510 fax: 301-975-3670</span><o:p></o:p></p>
<p class="MsoNormal"><span style="font-size:10.0pt;font-family:"Arial","sans-serif"">email:
<a href="mailto:karl.irikura@nist.gov"><span style="color:blue">karl.irikura@nist.gov</span></a></span><o:p></o:p></p>
<p class="MsoNormal"><span style="font-size:10.0pt;font-family:"Arial","sans-serif""><a href="http://www.nist.gov/mml/csd/informatics_research/index.cfm"><span style="color:blue">http://www.nist.gov/mml/csd/informatics_research/index.cfm</span></a>
</span><o:p></o:p></p>
<p class="MsoNormal"><span style="font-size:10.0pt;font-family:"Arial","sans-serif"">-------------------------------------------------------------------</span><o:p></o:p></p>
<p class="MsoNormal"><o:p> </o:p></p>
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