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</o:shapelayout></xml><![endif]--></head><body lang=KO link=blue vlink=purple><div class=WordSection1><p class=MsoNormal><span lang=EN-US>Dear molpro user, Recently I made an MRCI calculation for atoms like, B, C, Li, and so on. I found two problems<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US><o:p> </o:p></span></p><p class=MsoListParagraph style='margin-left:38.0pt;mso-para-margin-left:0gd;text-indent:-18.0pt;mso-list:l0 level1 lfo1'><![if !supportLists]><span lang=EN-US><span style='mso-list:Ignore'>1.<span style='font:7.0pt "Times New Roman"'> </span></span></span><![endif]><span lang=EN-US>There are ghost states.<o:p></o:p></span></p><p class=MsoListParagraph style='margin-left:38.0pt;mso-para-margin-left:0gd;text-indent:-18.0pt;mso-list:l0 level1 lfo1'><![if !supportLists]><span lang=EN-US><span style='mso-list:Ignore'>2.<span style='font:7.0pt "Times New Roman"'> </span></span></span><![endif]><span lang=EN-US>The calculated energies are sometimes lower than the experimental values.<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US><o:p> </o:p></span></p><p class=MsoNormal><span lang=EN-US>Examination of ci vectors reveals that the ghost states come from the insufficient specification of the symmetry. With C2v symmetry, 2pz and 2px have different energies.<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> Is there any method, options and so on for the imposition of strict restrictions so that two mentioned problems go away ? <o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US><o:p> </o:p></span></p><p class=MsoNormal><span lang=EN-US>Sincerely yours, Chun-Woo Lee<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US><o:p> </o:p></span></p><p class=MsoNormal><span lang=EN-US>**************************************************************************************************************************<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US>The energies of the first several valence states of a carbon atom are<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US><o:p> </o:p></span></p><p class=MsoNormal><span lang=EN-US>State E Exc. E (eV)<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> 3P(2S22P2) -37.78810854 0.000<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> 1D -37.74193738 1.256 (ghost state) <o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> 1D(2S22P2) -37.74187641 1.258 (lower than exptl. Value 1.260)<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> 1S(2S22P2) -37.68995308 2.671<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> 5S(2S2P3) -37.63521157 4.161 (lower than exptl. Value 4.179)<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> 3D(2S2P3) -37.49527426 7.968 <o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US><o:p> </o:p></span></p><p class=MsoNormal><span lang=EN-US>The script file I used to obtain the above energies for the valence states of a carbon atom is as follows:<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US><o:p> </o:p></span></p><p class=MsoListParagraph style='margin-left:38.0pt;mso-para-margin-left:0gd;text-indent:-18.0pt;mso-list:l1 level1 lfo2'><![if !supportLists]><span lang=EN-US><span style='mso-list:Ignore'>1.<span style='font:7.0pt "Times New Roman"'> </span></span></span><![endif]><span lang=EN-US>The basis set is basically av6z with i orbitals removed and the diffuse component of h orbital is removed<o:p></o:p></span></p><p class=MsoListParagraph style='margin-left:38.0pt;mso-para-margin-left:0gd;text-indent:-18.0pt;mso-list:l1 level1 lfo2'><![if !supportLists]><span lang=EN-US><span style='mso-list:Ignore'>2.<span style='font:7.0pt "Times New Roman"'> </span></span></span><![endif]><span lang=EN-US>Active space (1s,2s,2p,3d) <o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US><o:p> </o:p></span></p><p class=MsoNormal><span lang=EN-US>************ the script file ********************************************************************************<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US><o:p> </o:p></span></p><p class=MsoNormal><span lang=EN-US>***,C 6 valence states with (1s,2s,2p,3d) and 4 Rydberg states with (1s,2s,2p,3d,3s)<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US>memory, 50, mw<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US>!gprint,basis,orbital,civector<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US>symmetry,x,y<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US>geometry = {C}<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> basis= {s, C , 312100.0000000, 46740.0000000, 10640.0000000, 3013.0000000, 982.8000000, 354.8000000, 138.4000000, 57.3500000, 24.9200000, 11.2300000, 5.2010000, 2.4260000, 0.9673000, 0.4456000, 0.1971000, 0.0863500, 0.03540<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> c, 1.11, 0.00000567, 0.00004410, 0.00023190, 0.00097897, 0.00355163, 0.01144061, 0.03299855, 0.08405347, 0.18067613, 0.30491140, 0.34141570<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> c, 1.11, -0.00000121, -0.00000939, -0.00004947, -0.00020857, -0.00076015, -0.00245469, -0.00720153, -0.01880742, -0.04325001, -0.08259733, -0.12857592<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> p, C , 295.2000000, 69.9800000, 22.6400000, 8.4850000, 3.4590000, 1.5040000, 0.6783000, 0.3087000, 0.1400000, 0.0617800, 0.02376<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> c, 1.5, 0.00014249, 0.00122010, 0.00633696, 0.02351875, 0.06990447<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> d, C , 4.5420000, 1.9790000, 0.8621000, 0.3756000, 0.1636000, 0.06360<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> f, C , 2.6310000, 1.2550000, 0.5988000, 0.2857000, 0.1180<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> g, C , 2.6520000, 1.2040000, 0.5470000, 0.2540<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> h, C , 2.0300000, 0.8511000, 0.4510}<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US><o:p> </o:p></span></p><p class=MsoNormal><span lang=EN-US> $states =[3P(2s22p2),1D,1D(2s22p2),1S(2s22p2),5S(2s2p3),3D(2s2p3)];<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> <o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> hf<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> {multi;occ,5,2,2,1;frozen,1.1;wf,6,4,2;state,1;wf,6,1,0;state,3;wf,6,4,0;state,3<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> wf,6,1,4;state,1;wf,6,4,4;state,1;wf,6,1,2;state,2;wf,6,4,2;state,2}<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> {mrcic;occ,5,2,2,1;wf,6,4,2}<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> e(1) = energy<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> {ci,nocheck;wf,6,1,0;state,3,1,2,3}<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> e(2) = energy(1)<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> e(3) = energy(2)<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> e(4) = energy(3)<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> {mrcic;wf,6,4,4}<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> e(5) = energy<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> {ci;wf,6,4,2;state,1,2}<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> e(6) = energy<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> <o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> de = (e-e(1))*toev<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> <o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> {table,states,e,de<o:p></o:p></span></p><p class=MsoNormal><span lang=EN-US> head,'State','E','Exc. E (eV)'}<o:p></o:p></span></p></div></body></html>