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<body class='hmmessage'><div dir='ltr'>Dear Molpro Experts,<div><br></div><div>I tried to calculate RS2 (CASPT2) gradient using a converged CAS(10,10) wavefunction for a molecule in Ci symmetry. The basis sets used were def2-TZVP (and def2-TZVP/JKFIT for density fitting). The CASSCF part converged nicely, however, the calculation stuck at RS2 part for a long time without any further output. I issued 24GB of memory and 16 cpu OpenMP parallel on a dual E5-2680 computer so this should not be a resource problem. Also another NEVPT2 calculation based on the same CASSCF wavefunction without density fitting was able to finish normally without any error, while non-DF RS2 based on the same CASSCF calculation also stuck. </div><div><br></div><div>The input file is:</div><div><div><font face="Courier New" size="2">***,MOLPRO CASPT2 Job</font></div><div><font face="Courier New" size="2">memory,3000,m</font></div><div><font face="Courier New" size="2">start;</font></div><div><font face="Courier New" size="2">symmetry,auto</font></div><div><font face="Courier New" size="2">bohr</font></div><div><font face="Courier New" size="2">geomtyp=xyz</font></div><div><font face="Courier New" size="2">geometry={</font></div><div><font face="Courier New" size="2">14</font></div><div><font face="Courier New" size="2">MOLPRO Job DF-RS2</font></div></div><div><font face="Courier New" size="2">.......</font></div><div><font face="Courier New" size="2">..... molecular specifications in XYZ</font></div><div><font face="Courier New" size="2">.......</font></div><div><font face="Courier New" size="2">}</font></div><div><font face="Courier New" size="2"><br></font></div><div><div><font face="Courier New" size="2">basis={default=def2-TZVP</font></div><div><font face="Courier New" size="2"> set,fit</font></div><div><font face="Courier New" size="2"> default,def2-TZVP/JKFIT}</font></div><div><font face="Courier New" size="2">{cfit,basis=fit}</font></div></div><div><font face="Courier New" size="2"><br></font></div><div><div><font face="Courier New" size="2">{MATROP ! read orbitals from previous CASSCF</font></div><div><font face="Courier New" size="2"> read,matroporb,file=rs2.nat</font></div><div><font face="Courier New" size="2"> save,matroporb,2140.2,orbitals}</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2">!CAS(10,10)</font></div><div><font face="Courier New" size="2">{df-multi,energy=1.0e-8,gradient=1.0e-5,step=1.0e-5</font></div><div><font face="Courier New" size="2"> maxit,40</font></div><div><font face="Courier New" size="2"> occ,27,25; ! RHF occ 24,23</font></div><div><font face="Courier New" size="2"> closed,21,21;</font></div><div><font face="Courier New" size="2"> wf,94,1,0;</font></div><div><font face="Courier New" size="2"> start,2140.2</font></div><div><font face="Courier New" size="2"> natorb,2141.2,print=20,ci,state=1.1</font></div><div><font face="Courier New" size="2">}</font></div></div><div><font face="Courier New" size="2"><br></font></div><div><div><font face="Courier New" size="2">{df-RS2,thrden=1.0d-11,thrvar=1.0d-11,maxit=100,maxiti=100</font></div><div><font face="Courier New" size="2"> occ,27,25;</font></div><div><font face="Courier New" size="2"> closed,21,21;</font></div><div><font face="Courier New" size="2"> wf,94,1,0;</font></div><div><font face="Courier New" size="2"> orbit,2141.2;</font></div><div><font face="Courier New" size="2"> state,1,1;</font></div><div><font face="Courier New" size="2">}</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2">forces;</font></div><div><font face="Courier New" size="2">---</font></div></div><div><br></div><div>The CASSCF(10,10) part finished without any problems.</div><div><div><font face="Courier New" size="2"><div> NUCLEAR CHARGE: 94</div><div> NUMBER OF PRIMITIVE AOS: 558</div><div> NUMBER OF SYMMETRY AOS: 508</div><div> NUMBER OF CONTRACTIONS: 312 ( 156Ag + 156Au )</div><div> NUMBER OF CORE ORBITALS: 24 ( 12Ag + 12Au )</div><div> NUMBER OF VALENCE ORBITALS: 42 ( 21Ag + 21Au )</div><div><br></div><div> NUCLEAR REPULSION ENERGY 828.85467872</div><div><br></div></font></div><div><font face="Courier New" size="2"> Basis set: FIT</font></div><div><font face="Courier New" size="2"> Basis size: 1094</font></div><div><font face="Courier New" size="2"> Attributes:</font></div><div><font face="Courier New" size="2"> Sphericals: T</font></div><div><font face="Courier New" size="2">1PROGRAM * MULTI (Direct Multiconfiguration SCF) Authors: P.J. Knowles, H.-J. Werner (1984) S.T. Elbert (1988)</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"> (Density-fitting MCSCF) Authors: W. Gyorffy and T. Shiozaki (2012)</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"> Number of closed-shell orbitals: 42 ( 21 21 )</font></div><div><font face="Courier New" size="2"> Number of active orbitals: 10 ( 6 4 )</font></div><div><font face="Courier New" size="2"> Number of external orbitals: 260 ( 129 131 )</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"> State symmetry 1</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"> Number of electrons: 10 Spin symmetry=Singlet Space symmetry=1</font></div><div><font face="Courier New" size="2"> Number of states: 1</font></div><div><font face="Courier New" size="2"> Number of CSFs: 9772 (31824 determinants, 63504 intermediate states)</font></div></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"><...skip...></span></div><div><div><font face="Courier New" size="2"> Number of orbital rotations: 6968 ( 210 Core/Active 5460 Core/Virtual 0 Active/Active 1298 Active/Virtual)</font></div><div><font face="Courier New" size="2"> Total number of variables: 38792</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"> ITER. MIC NCI NEG ENERGY(VAR) ENERGY(PROJ) ENERGY CHANGE GRAD(0) GRAD(ORB) GRAD(CI) STEP TIME</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"> 1 54 31 0 -2383.67887780 -2383.67887791 -0.00000012 0.00089353 0.00000000 0.00000090 0.19D-03 1100.72</font></div><div><font face="Courier New" size="2"> 2 39 12 0 -2383.67887791 -2383.67887791 0.00000000 0.00000035 0.00000002 0.00000083 0.15D-05 1898.73</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"> ** WVFN **** CONVERGENCE REACHED, FINAL GRADIENT: 0.58D-07</font></div></div><div><font face="Courier New" size="2"><...skip...></font></div><div><div><font face="Courier New" size="2"> CI vector</font></div><div><font face="Courier New" size="2"> =========</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"> 220000 2220 0.8981314</font></div><div><font face="Courier New" size="2"> 222000 2200 -0.1354345</font></div><div><font face="Courier New" size="2"> 200000 2222 -0.1345665</font></div><div><font face="Courier New" size="2"> 220200 2020 -0.1324518</font></div><div><font face="Courier New" size="2"> 2b0b00 2a2a -0.0898835</font></div><div><font face="Courier New" size="2"> 2a0a00 2b2b -0.0898835</font></div><div><font face="Courier New" size="2"> 2aa000 22bb -0.0887362</font></div><div><font face="Courier New" size="2"> 2bb000 22aa -0.0887362</font></div><div><font face="Courier New" size="2"> 22ba00 2ba0 0.0783718</font></div><div><font face="Courier New" size="2"> 22ab00 2ab0 0.0783718</font></div><div><font face="Courier New" size="2"> 2b0a00 2b2a 0.0637264</font></div><div><font face="Courier New" size="2"> 2a0b00 2a2b 0.0637264</font></div><div><font face="Courier New" size="2"> 220020 0220 -0.0629049</font></div><div><font face="Courier New" size="2"> 2ba000 22ba 0.0608414</font></div><div><font face="Courier New" size="2"> 2ab000 22ab 0.0608414</font></div><div><font face="Courier New" size="2"> 22b0a0 b2a0 0.0556144</font></div><div><font face="Courier New" size="2"> 22a0b0 a2b0 0.0556144</font></div><div><font face="Courier New" size="2"> 220ab0 ab20 0.0555299</font></div><div><font face="Courier New" size="2"> 220ba0 ba20 0.0555299</font></div></div><div><div><font face="Courier New" size="2"> 2a00a0 b22b -0.0517008</font></div><div><font face="Courier New" size="2"> 2b00b0 a22a -0.0517008</font></div><div><font face="Courier New" size="2"><br></font></div><div><font face="Courier New" size="2"> TOTAL ENERGIES -2383.67887791</font></div></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"><...skip...></span></div><div><br></div><div>However, the DF-RS2 part that followed stuck at the status shown below without any further outputs for more than 20 hours, not to mention the next calculation of its analytic gradients. </div><div><br></div><div><div><font size="2" face="Courier New"> Basis set: FIT</font></div><div><font size="2" face="Courier New"> Basis size: 1094</font></div><div><font size="2" face="Courier New"> Attributes:</font></div><div><font size="2" face="Courier New"> Sphericals: T</font></div><div><font size="2" face="Courier New"><b>1PROGRAM * RS2 (Multireference RS Perturbation Theory) Authors: H.-J. Werner (1993), P. Celani (1998)</b></font></div><div><font size="2" face="Courier New"><b><br></b></font></div><div><font size="2" face="Courier New"><b> (Density-fitting CASPT2) Authors: W. Gyorffy and T. Shiozaki (2012)</b></font></div><div><font size="2" face="Courier New"><b><br></b></font></div><div><font size="2" face="Courier New"><b> Convergence thresholds: THRVAR = 1.00D-11 THRDEN = 1.00D-11</b></font></div><div><font size="2" face="Courier New"><b><br></b></font></div><div><font size="2" face="Courier New"><b> Number of optimized states: 1 Roots: 1</b></font></div><div><font size="2" face="Courier New"><b> Number of reference states: 1 Roots: 1</b></font></div><div><font size="2" face="Courier New"><b><br></b></font></div><div><font size="2" face="Courier New"><b> Using ITF DF-MP2 gradient implementation</b></font></div></div><div><br></div><div>Switching back to non-DF calculations did not solve the problem. The CASSCF and NEVPT2 single point calculations could finish normally and quickly, while the non-DF RS2 still stuck at the same place.</div><div><br></div><div><div> <font size="2" face="Courier New">PROGRAM * NEVPT (Multireference Perturbation Theory)</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Convergence thresholds: THRVAR = 1.00D-11 THRDEN = 1.00D-11</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Number of optimized states: 1 Roots: 1</span></div><div><font size="2" face="Courier New"> Number of reference states: 1 Roots: 1</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Reference symmetry: 1 Singlet</span></div><div><font size="2" face="Courier New"> Number of electrons: 94</font></div><div><font size="2" face="Courier New"> Maximum number of shells: 7</font></div><div><font size="2" face="Courier New"> Maximum number of spin couplings: 132</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Reference space: 4521 conf 9772 CSFs</span></div><div><font size="2" face="Courier New"> N elec internal: 4521 conf 9772 CSFs</font></div><div><font size="2" face="Courier New"> N-1 el internal: 8350 conf 27720 CSFs</font></div><div><font size="2" face="Courier New"> N-2 el internal: 6765 conf 34650 CSFs</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Number of electrons in valence space: 46</span></div><div><font size="2" face="Courier New"> Maximum number of open shell orbitals in reference space: 10</font></div><div><font size="2" face="Courier New"> Maximum number of open shell orbitals in internal spaces: 12</font></div></div><div><div><font size="2" face="Courier New"> Number of core orbitals: 24 ( 12 12 )</font></div><div><font size="2" face="Courier New"> Number of closed-shell orbitals: 18 ( 9 9 )</font></div><div><font size="2" face="Courier New"> Number of active orbitals: 10 ( 6 4 )</font></div><div><font size="2" face="Courier New"> Number of external orbitals: 260 ( 129 131 )</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Molecular orbitals read from record 2142.2 Type=MCSCF/NATURAL (state 1.1)</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Coulomb and exchange operators available. No transformation done.</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Number of p-space configurations: 56</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Reference wavefunction optimized for reference space (refopt=1)</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> State Reference Energy</span></div><div><font size="2" face="Courier New"> 1 -2383.67915818</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Number of internal configurations: 9772</span></div><div><font size="2" face="Courier New"> Number of singly external configurations: 0</font></div><div><font size="2" face="Courier New"> Number of doubly external configurations: 0</font></div><div><font size="2" face="Courier New"> Total number of contracted configurations: 9772</font></div><div><font size="2" face="Courier New"> Total number of uncontracted configurations: 9772</font></div></div><div><div><font size="2" face="Courier New"> Weight factors for SA-density in H0: 1.000000</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> FIMAX= 0.16D+00 FXMAX= 0.33D+02 DIAG= F F NOREF=1 NOINT=2 IHPPD=2</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Nuclear energy: 828.85467872</span></div><div><font size="2" face="Courier New"> Core energy: -2940.82861073</font></div><div><font size="2" face="Courier New"> Zeroth-order valence energy: -27.53507067</font></div><div><font size="2" face="Courier New"> Zeroth-order total energy: -2139.50900267</font></div><div><font size="2" face="Courier New"> First-order energy: -244.17015551</font></div></div><div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Number of irreps: 2</span></div><div><font size="2" face="Courier New"> Number of frozen orbitals: 12 12</font></div><div><font size="2" face="Courier New"> Number of inactive orbitals: 21 21</font></div><div><font size="2" face="Courier New"> Number of occupied orbitals: 27 25</font></div><div><font size="2" face="Courier New"> Number of valence orbitals: 15 13</font></div><div><font size="2" face="Courier New"> Number of external orbitals: 129 131</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Number of alpha electrons: 5</span></div><div><font size="2" face="Courier New"> Number of beta electrons: 5</font></div><div><font size="2" face="Courier New"> Multiplicity: 1</font></div><div><font size="2" face="Courier New"> Number of states: 1</font></div><div><font size="2" face="Courier New"> Number of determinants: 31824</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Number of total orbitals: 288</span></div><div><font size="2" face="Courier New"> Number of core orbitals: 18</font></div><div><font size="2" face="Courier New"> Number of active orbitals: 10</font></div><div><font size="2" face="Courier New"> Number of virtual orbitals: 260</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> **STARTING THE DENSITY MATRICES CALCULATION**</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> CPU time for the density matrices calculation: 169.41 secs.</span></div></div><div><div><font size="2" face="Courier New"> Building up Koopmans matrices</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> KoopE has taken: 0.00 secs.</span></div><div><font size="2" face="Courier New"> Koop2E has taken: 0.50 secs.</font></div><div><font size="2" face="Courier New"> Koop0pE has taken: 1.65 secs.</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Checking elements of F matrix</span></div><div><font size="2" face="Courier New"> Maximum value of the F matrix is: 0.8704349182D-08</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Building matrix AMAT</span></div></div><div><div><font size="2" face="Courier New"> BAMAT has taken: 102.62 secs.</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Building matrix BMAT</span></div><div><font size="2" face="Courier New"> BBMAT has taken: 0.46 secs.</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Building matrix CMAT</span></div><div><font size="2" face="Courier New"> BCMAT has taken: 1.58 secs.</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Largest difference between BMAT and CMAT : 0.5320559943D-07</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Largest difference between BTMAT and CTMAT: 0.5320559726D-07</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Total CPU time for Koopro4: 277.04 secs.</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> **STARTING THE PERTURBATIVE CALCULATION**</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> Maximum of off-diagonal core Fock matrix is: 0.4170875439D-09</span></div><div><font size="2" face="Courier New"> Maximum of off-diagonal virtual Fock matrix is: 0.1052481504D-08</font></div></div><div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> CPU time for V(0) 0.09 secs.</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> CPU time for V(+1) 0.12 secs.</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> CPU time for V(-1) 0.29 secs.</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> CPU time for V(+2) 0.03 secs.</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> CPU time for V(-2) 0.10 secs.</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> CPU time for V(0)' 2.02 secs.</span></div></div><div><div><font size="2" face="Courier New"> CPU time for V(-1)' 16.72 secs.</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> CPU time for V(+1)' 12.19 secs.</span></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> SC and PC correlation energy for each class</span></div><div><font size="2" face="Courier New"> =================================================================</font></div><div><font size="2" face="Courier New"> Using H Dyall</font></div><div><font size="2" face="Courier New"> =================================================================</font></div><div><font size="2" face="Courier New"> Norm SC Energy SC Norm PC Energy PC</font></div><div><font size="2" face="Courier New"> (0) 0.2768641960 -0.9510166330 0.2768641960 -0.9510166330</font></div><div><font size="2" face="Courier New"> (+1) 0.0261897554 -0.0653943833 0.0263229796 -0.0654967075</font></div><div><font size="2" face="Courier New"> (-1) 0.0536273643 -0.1680576257 0.0538969350 -0.1682657199</font></div><div><font size="2" face="Courier New"> (+2) 0.0025936655 -0.0056460593 0.0026248742 -0.0056694796</font></div><div><font size="2" face="Courier New"> (-2) 0.0165171161 -0.0749480177 0.0167960046 -0.0752581146</font></div><div><font size="2" face="Courier New"> (+1)' 0.0015687187 -0.0031541628 0.0018816982 -0.0033382817</font></div><div><font size="2" face="Courier New"> (-1)' 0.0080081528 -0.0222789233 0.0094632751 -0.0231687787</font></div><div><font size="2" face="Courier New"> (0)' 0.0574059521 -0.1020098507 0.0612787166 -0.1036343115</font></div><div><font size="2" face="Courier New"> =================================================================</font></div><div><font size="2" face="Courier New"> Total 0.4427749210 -1.3925056558 0.4491286793 -1.3958480264</font></div></div><div><div><font size="2" face="Courier New"> Total CPU time for dypc: 31.58 secs.</font></div><div><span style="font-family: 'Courier New'; font-size: 10pt;"> !NEVPT2 STATE 1.1 Energy -2385.075006209327</span></div><div><font size="2" face="Courier New"> Strongly contracted energy -2385.071663838717</font></div></div><div><br></div><div>The non-DF RS2 part still stucks at the same place, without mentioning ITF DF-MP2:</div><div><br></div><div><div><font size="2" face="Courier New"><b>1PROGRAM * RS2 (Multireference RS Perturbation Theory) Authors: H.-J. Werner (1993), P. Celani (1998)</b></font></div><div><b><br></b></div><div><font size="2" face="Courier New"><b> Convergence thresholds: THRVAR = 1.00D-11 THRDEN = 1.00D-11</b></font></div><div><font size="2" face="Courier New"><b><br></b></font></div><div><font size="2" face="Courier New"><b> Number of optimized states: 1 Roots: 1</b></font></div><div><font size="2" face="Courier New"><b> Number of reference states: 1 Roots: 1</b></font></div></div><div><br></div><div><b>May I request for some advise about what I did wrong with the RS2/DF-RS2 calculations?</b></div><div><b>Thank you very much !</b></div><div><br></div><div><div style="line-height: 21px; color: rgb(68, 68, 68); font-size: 15px;">==========</div><div style="line-height: 21px; color: rgb(68, 68, 68); font-size: 15px;">MJ Wu</div></div><div><br></div> </div></body>
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