CCL: GAMESS:SCF-Problem with DFT



 Sent to CCL by: Gustavo Mercier [gamercier::yahoo.com]
 Hi!
 Several points:
 1. Normally if you go with DIIS then Damping and Vshifting is turned off. Look
 at the REF.doc in the Gamess distribution where they give hints
 for helping in convergence. They also make a suggestion in
 the INPUT.doc under the SCF namelist where they suggest using ETHRESH
 and
 SWDIIS. I do not recommend the SWDIIS option because what it does is switch
 from DIIS to the second order method (SOSCF), and this has not worked out as
 well for me.
 2. Set ETHRESH (option under SCF) to a large value like 2E+0. This
 will make DIIS kick in early, and should stay on pretty much all the time.
 3. Another thing is the number of points used for computing the functional
 integrals. This is done numerically and is controled by the DFT namelist.
 The program uses a low number of points in the early iterations, and then
 switches to the full grid. I find that I have to start the full grid
 earlier. I've also had to use larger than default values and go up to 434 and
 590. I do work on Mn coordination complexes and they seem to be fairly soft with
 a fairly flat potential energy curve. Read under REF.doc details about the
 grids and expected accuracy in the energy gradients.
 I would also recommend doing the geometry optimization with delocalized
 coordinates:
 $ZMAT DELOC=.T. AUTO=.T. $END
 you also need to specify the number of variables in the $CONTRL namelist
 using (I believe) NZVAR=3*N-6 where N is the number of atoms.
 This will reduce the number of iterations and I find that it makes for a smarter
 optimization.
 On another note... if you intend to do thermochemistry, I've found that the
 'approximate' hessian kicked out at the end of the geometry optimization is not
 bad. For DFT the second derivatives are computed using numerical methods from
 (mostly) analytic gradients. Seems tha the augmented hessian methods that are
 used for default in geometry optimizations do a good job at getting the hessian
 ok, or at least as good as the default one-point numerical differentiation
 formula.
 Hope this helps!
 --
 Gustavo A. Mercier, Jr., MD, PhD
 gamercier,+,yahoo.com
 Gustavo.Mercier,+,bmc.org
 gumercie,+,bu.edu
 617-414-6440
 ----- Original Message ----
 > From: Rudolf Herrmann rudolf.herrmann__physik.uni-augsburg.de
 <owner-chemistry,+,ccl.net>
 > To: "Mercier, Gustavo, " <gamercier,+,yahoo.com>
 > Sent: Mon, December 21, 2009 6:42:44 AM
 > Subject: CCL: GAMESS:SCF-Problem with DFT
 >
 >
 > Sent to CCL by: "Rudolf Herrmann"
 [rudolf.herrmann:+:physik.uni-augsburg.de]
 > Hello all,
 > I'm using GAMESS(US), rev. R3 from Jan 12, 2009. I encountered a problem
 > in obtaining SCF with DFT. Part of the input:
 >
 > $CONTRL SCFTYP=UHF MULT=2 RUNTYP=Optimize COORD=unique INTTYP=HONDO $END
 > $CONTRL DFTTYP=PBE0  MAXIT=200 ICHARG=0  ECP=SBKJC  $END
 > $SYSTEM TIMLIM=80000 MEMORY=80000000 $END
 > $SCF DIRSCF=.T. DAMP=.T. SHIFT=.T. DIIS=.T. SOSCF=.F.  $END
 > $BASIS  GBASIS=SBKJC  $END
 > $STATPT OPTTOL=0.0001 NSTEP=200  $END
 > $GUESS  GUESS=HUCKEL  $END
 > $DATA
 > 4*Fuenfring - Phthalo  cctt als Cu-Komplex UHF
 > C1
 > C  6.0  -5.216897    -0.910406  -10.919197
 > .......  (many atoms)
 >
 > And that is the result of the first SCF calculation:
 >
 >                    
                      
                      
                
 >                    
           NONZERO
 >
 >
 >
 >
 > BLOCKS
 > ITER EX      TOTAL ENERGY        E
 CHANGE  DENSITY CHANGE    DIIS ERROR 
 >   VIR. SHIFT      DAMPING       
 INTEGRALS    SKIPPED
 >   1  0    -1036.5378101022 -1036.5378101022 
 1.230919053  0.821519137 
 >   0.000000000    1.000000000    6231081460 
 193615138
 >           * * *  INITIATING DIIS
 PROCEDURE  * * *
 >   2  1    -1041.6461370603   
 -5.1083269581  11.464555047  0.402615779 
 >   0.000000000    1.000000000    6236128017 
 193099683
 >   3  2    -1002.7358262561   
 38.9103108042  11.474994560  1.302218004 
 >   0.000000000    1.000000000    6241249413 
 191679251
 >   4  3    -1041.8568160646  -39.1209898086 
 0.195994971  0.402579497 
 >   0.000000000    1.000000000    6237469221 
 191939968
 >   5  4    -1042.3054537170   
 -0.4486376523  0.226115870  0.343346341 
 >   0.000000000    1.000000000    6057043846 
 201451242
 >   6  5    -1042.6171017767   
 -0.3116480597  0.279322397  0.266341119 
 >   0.000000000    1.000000000    6061097833 
 201455155
 >   7  6    -1042.9966679031   
 -0.3795661264  0.106460306  0.081821934 
 >   0.000000000    1.000000000    6077977863 
 201147673
 >   8  7    -1043.0591297051   
 -0.0624618020  0.046857045  0.011477052 
 >   0.000000000    1.000000000    5989046608 
 202974307
 >   9  8    -1043.0669450821   
 -0.0078153770  0.011381853  0.005948448 
 >   0.000000000    1.000000000    5736168713 
 207005748
 >   10  9    -1043.0697884590   
 -0.0028433770  0.013485505  0.004417363 
 >   0.000000000    1.000000000    5475629752 
 210127430
 >   11 10    -1043.0723408038    -0.0025523448 
 0.017067266  0.003869563 
 >   0.000000000    1.000000000    5458702402 
 210313186
 >   12 11    -1043.0751463423    -0.0028055385 
 0.014434645  0.003675831 
 >   0.000000000    1.000000000    5453595333 
 210460303
 >   13 12    -1043.0777030610    -0.0025567187 
 0.019791837  0.003849315 
 >   0.000000000    1.000000000    5397573182 
 211084337
 >   14 13    -1043.0813673308    -0.0036642698 
 0.004903916  0.004281832 
 >   0.000000000    1.000000000    5491928111 
 210122347
 > CONVERGED TO SWOFF, SO DFT CALCULATION IS NOW SWITCHED ON.
 >           * * *  INITIATING DIIS
 PROCEDURE  * * *
 >   15 14    -1058.1568375748  -15.0754702440 
 1.625183076  0.052558260 
 >   6225076316  194161508
 >   16 15    -1056.2538409178    1.9029966571 
 0.866868728  0.796456193 
 >   6203667374  195873448
 >   17 16    -1058.5031727428    -2.2493318250 
 0.157468336  0.035593489 
 >   6097769151  200991564
 >   18 17    -1058.2872778511    0.2158948917 
 0.070399380  0.134520819 
 >   6058543947  201342138
 >   19 18    -1058.5442781186    -0.2570002675 
 0.113766853  0.013742123 
 >   5927217989  204237218
 >   20 19    -1058.5522842356    -0.0080061170 
 0.023549798  0.007512045 
 >   5840741652  205391057
 >   21 20    -1058.5530282008    -0.0007439652 
 0.017420717  0.010226036 
 >   5670929315  208075365
 >   22 21    -1058.5559993807    -0.0029711799 
 0.047523393  0.009589402 
 >   5564367770  209481859
 >   23 22    -1058.5585808178    -0.0025814371 
 0.029346400  0.024600824 
 >   5707543406  207871809
 >   24 23    -1058.5575623133    0.0010185045 
 0.013103014  0.017673475 
 >   5514532287  210353312
 > NEXT ENERGY RISES: SWITCHING DIIS OFF FOR  5 ITERS, NEW ETHRSH=
 1.59E-02
 >   25 24    -1058.5566503140    0.0009119993 
 0.065560927  0.026774000 
 >   5383825524  211393480
 >   26 25    -1058.5245291667    0.0321211473 
 0.955346110  0.097075114 
 >   5824682851  206204169
 >   27 26    -1045.4354021475    13.0891270192 
 19.549841437  1.414811739 
 >   6176465140  198256544
 >   28 27    -820.5152084492  224.9201936983
 183.173769694  2.570654172 
 >   6246989834  190654722
 >   29 28      615.6159645678 
 1436.13117301703000.606626971  2.010533226 
 >   6254865291  185798793
 >   30 29    1752.6067873608 
 1136.99082279303001.172518613  10.378186893 
 >   6256392203  177999716
 >   31 30    1765.6511795332   
 13.04439217243095.179109875  2.823919783 
 >   6256414149  176971112
 >   32 31    2820.6124946084 
 1054.96131507523095.984312651  2.819419434 
 >   6256313973  177970697
 >   33 32    2012.2921032636 
 -808.32039134473958.491129374  3.341335928 
 >   6256340795  177974590
 >   34 33    3111.0312907781 
 1098.73918751453958.190267766  2.732484925 
 >   6256322037  177808512
 >   35 34    2059.9131221528
 -1051.11816862534124.537686577  3.295129177 
 >   6256330123  177699772
 > ....... and so on (oscillates).
 >
 > My question is: Everything seems reasonable until the program's decision
 > to turn off DIIS for five iterations. How can I switch off this behaviour?
 > I did not find any hint in the manual (maybe I have simply overlooked it).
 >
 > Thanks a lot for suggestions.
 >
 > Merry Christmas and lots of successful calculations in the New Year!
 >
 > R. Herrmann.
 >
 > --
 > Dr. Rudolf Herrmann
 > Institut für Physik
 > Universität Augsburg
 > Universitätsstr. 1
 > D-86159 Augsburg
 >
 >
 >
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