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<body class='hmmessage'><div dir='ltr'>Dear Molpro Experts,<div><br></div><div>I tried to do geometry optimization at df-CASSCF level, and wished the job to run using analytic gradient via df-RS2 with "noexc" keyword:(reference: <a href="http://www.molpro.net/pipermail/molpro-user/2012-October/005092.html" target="_blank" style="font-size: 12pt;">http://www.molpro.net/pipermail/molpro-user/2012-October/005092.html</a></div><div><span style="font-size: 12pt;">)</span></div><div>However, the geometry optimization still proceeded with numerical gradient. Here is my input:</div><div><br></div><div><div><font face="Courier New, sans-serif">***,df-CAS(12,12) optimization</font></div><div><font face="Courier New, sans-serif">memory,15000,m</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif">cartesian</font></div><div><font face="Courier New, sans-serif">basis=6-31G*</font></div></div><div><div><font face="Courier New, sans-serif">geomtyp=xyz</font></div><div><font face="Courier New, sans-serif">geometry={</font></div><div><font face="Courier New, sans-serif">39</font></div><div><font face="Courier New, sans-serif">TS optimization</font></div><div><font face="Courier New, sans-serif"> C -4.85773400 0.51429900 0.42945500</font></div><div><font face="Courier New, sans-serif"> .... atomic coordinates follows ...</font></div></div><div><div><font face="Courier New, sans-serif"> H 0.73880900 2.27415000 -0.56530600</font></div><div><font face="Courier New, sans-serif">}</font></div></div><div><div><font face="Courier New, sans-serif">! orbital from previous df-CAS/6-31G*</font></div><div><font face="Courier New, sans-serif">{matrop</font></div><div><font face="Courier New, sans-serif">read,oldorbitals,file=radical_df4.orb</font></div><div><font face="Courier New, sans-serif">save,oldorbitals,2140.2,orbitals}</font></div></div><div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif">{df-multi,DF_BASIS=vdz/JKFIT</font></div><div><font face="Courier New, sans-serif">start,2140.2</font></div><div><font face="Courier New, sans-serif">close,76</font></div><div><font face="Courier New, sans-serif">occ,88</font></div><div><font face="Courier New, sans-serif">wf,164,1,0</font></div><div><font face="Courier New, sans-serif">natorb,ci,print</font></div><div><font face="Courier New, sans-serif">orbital,2141.2</font></div><div><font face="Courier New, sans-serif">maxiter,39</font></div><div><font face="Courier New, sans-serif">}</font></div></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif">! change basis to VDZ with density fitting</font></div><div><div><font face="Courier New, sans-serif">basis={</font></div><div><font face="Courier New, sans-serif"> default,vdz</font></div><div><font face="Courier New, sans-serif"> set,fit ! defines a basis set called fit</font></div><div><font face="Courier New, sans-serif"> default,vdz/JKFIT} ! here uses slash in the basis name</font></div><div><font face="Courier New, sans-serif">{cfit,basis=fit} ! defines the DF basis set</font></div><div><font face="Courier New, sans-serif">spherical</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif">{df-multi</font></div><div><font face="Courier New, sans-serif">start,2141.2</font></div><div><font face="Courier New, sans-serif">close,76</font></div><div><font face="Courier New, sans-serif">occ,88</font></div><div><font face="Courier New, sans-serif">wf,164,1,0</font></div><div><font face="Courier New, sans-serif">natorb,ci,print</font></div><div><font face="Courier New, sans-serif">orbital,2142.2</font></div><div><font face="Courier New, sans-serif">maxiter,39</font></div><div><font face="Courier New, sans-serif">}</font></div></div><div><font face="Courier New, sans-serif"><br></font></div><div><div><font face="Courier New, sans-serif">! df-CAS analytic gradient using df-RS2 with keyword noexc</font></div><div><span style="font-size: 12pt;"><font face="Courier New, sans-serif">{df-RS2,thrden=1.0d-11,thrvar=1.0d-11,maxit=100,maxiti=100</font></span></div><div><font face="Courier New, sans-serif">core,75 ! this should be redundant with noexc</font></div><div><font face="Courier New, sans-serif">occ,88</font></div><div><font face="Courier New, sans-serif">close,76</font></div><div><font face="Courier New, sans-serif">noexc; ! this is just for analytic grad</font></div><div><font face="Courier New, sans-serif"> wf,164,1,0;</font></div><div><font face="Courier New, sans-serif">state,1,1</font></div><div><font face="Courier New, sans-serif">orbit,2142.2</font></div><div><font face="Courier New, sans-serif">}</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><span style="font-size: 12pt;"><font face="Courier New, sans-serif">optg,root=2 ! optimize for transition state</font></span></div></div><div><br></div><div>Everything went fine until df-RS2 finished, and the RSPT2 energy indeed equals to the CASSCF reference energy. But while starting geometry optimization, I found in the output file that the calculation still used numeric gradient.</div><div><span style="font-size: 12pt;"><br></span></div><div><span style="font-size: 12pt;">May I know what went wrong with the input file? The tail of the output file follows. Thank you very much for your help!</span></div><div><br></div><div>Sincerely,</div><div>MJ Wu</div><div><br></div><div><div><font face="Courier New, sans-serif"> <b>Reference energy -1293.32140467</b></font></div><div><font face="Courier New, sans-serif"> Nuclear energy 1881.75751251</font></div><div><font face="Courier New, sans-serif"> Kinetic energy 1292.96788162</font></div><div><font face="Courier New, sans-serif"> One electron energy -5511.10187574</font></div><div><font face="Courier New, sans-serif"> Two electron energy 2336.02295856</font></div><div><font face="Courier New, sans-serif"> Virial quotient -1.00027342</font></div><div><font face="Courier New, sans-serif"> Correlation energy 0.00000000</font></div><div><font face="Courier New, sans-serif"> <b>!RSPT2 STATE 1.1 Energy -1293.32140466</b>6142</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> !RSPT2 STATE 1.1 Dipole moment -1.75999116 -0.81167791 0.50501499</font></div><div><font face="Courier New, sans-serif"> Dipole moment /Debye -4.47315833 -2.06294434 1.28353600</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> Hylleraas correlation energy: 0.00000000</font></div><div><font face="Courier New, sans-serif"> <b>Total energy: -1293.32140467</b></font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> Solving MCSCF z-vector equations for state 1.1, requested accuracy= 0.10D-05</font></div><div><font face="Courier New, sans-serif"> Convergence reached in 4 iterations ( 4 expansion vectors), accuracy= 0.65D-06</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> Reference dipole moments: -1.75999116 -0.81167791 0.50501499</font></div><div><font face="Courier New, sans-serif"> !RSPT2 dipole moments (ED): -1.76000654 -0.81168150 0.50501620</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> RSPT2 Gradient info saved on record 5200.1</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> CPU-time for rhs: 703.84 sec</font></div><div><font face="Courier New, sans-serif"> CPU-time for cpmcscf: 3765.26 sec</font></div><div><font face="Courier New, sans-serif"> CPU-time for densities: 2.35 sec</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> **********************************************************************************************************************************</font></div><div><font face="Courier New, sans-serif"> DATASETS * FILE NREC LENGTH (MB) RECORD NAMES</font></div><div><font face="Courier New, sans-serif"> 1 25 7557.78 500 610 700 900 950 970 1001 129 960 1100</font></div><div><font face="Courier New, sans-serif"> VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S</font></div><div><font face="Courier New, sans-serif"> 1400 1410 1200 1210 1080 1600 1650 1700 1380 5200</font></div><div><font face="Courier New, sans-serif"> T V H0 H01 AOSYM SMH MOLCAS OPER JKOP RS2GRAD</font></div><div><font face="Courier New, sans-serif"> 5210 7009 90002 90003 7005 </font></div><div><font face="Courier New, sans-serif"> RS2GRAD ITF ITF</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> 2 7 18.73 700 1000 520 2140 2141 1001 2142</font></div><div><font face="Courier New, sans-serif"> GEOM BASIS MCVARS MATROP MCSCF BASIS MCSCF</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> PROGRAMS * TOTAL RS2 MULTI INT MULTI MATROP INT</font></div><div><font face="Courier New, sans-serif"> CPU TIMES * 42786.30 5427.08 21523.68 13.74 15548.16 2.63 266.23</font></div><div><font face="Courier New, sans-serif"> REAL TIME * 4057.84 SEC</font></div><div><font face="Courier New, sans-serif"> DISK USED * 78.76 GB</font></div><div><font face="Courier New, sans-serif"> **********************************************************************************************************************************</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> PROGRAM * OPT (Geometry optimization) Authors: F. Eckert and H.-J. Werner</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> Geometry optimization using default procedure for command DF-RS2</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> Geometry written to block 1 of record 700</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"><b> Generated 111 symmetrical displacements</b></font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"><b> Numerically approximating hessian using forward gradient differences</b></font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> Task list generated. Total number of displacements: 111</font></div><div><font face="Courier New, sans-serif"><br></font></div><div><font face="Courier New, sans-serif"> 11 tasks completed, CPU=3d 16h 28m 23s Elapsed=9h 25m 6s</font></div><div><font face="Courier New, sans-serif"> 22 tasks completed, CPU=7d 2h 25m 20s Elapsed=17h 49m 50s</font></div></div><div><br></div> </div></body>
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