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Re^2: Different results of SA-MCSCF calculations between Firefly 8.0 and 8.0.1

Alex Granovsky
gran@classic.chem.msu.su


Dear Panwang,
Dear Thom,

if I understand the problem correctly, it is related to state
tracking. Namely, with Firefly v. 8.0.1 state tracking remaps state
#2 to state #6 while with older versions of Firefly it does not.
The reason of this is most likely as follows. The first set of
reference CI vectors is prepared after first CI procedure i.e.
using original input MOs. With Firefly v. 8.0.1, CASSCF orbitals
are transformed to diagonalize current density matrix during first
MCSCF step, while previous versions of Firefly used other
canonicalization schemes. As old MOs come from older version of
Firefly, they will be rotated at the first MCSCF iteration.
As a result, starting MCSCF using old converged orbitals
may result to false state remaps caused by a sudden changes in
orbitals and hence CI vectors.

There are several workarounds to this problem.

First, one can resort to old style behavior as suggested by Thom.

Second, one can converge a single point MCSCF with state tracking disabled
to get new, rotated orbitals which can be used to start geometry
optimization (with tracking) with Firefly v. 8.0.1. Note, these
orbitals will be most likely bad starting guess for Firefly v. 8.0.0
due to exactly the same problem described above.

Hope this helps.

Kind regards,
Alex Granovsky







1. By default, Firefly v. 8.0.1 uses different orbitals



On Wed Jan 15 '14 1:01pm, Thomas Pijper wrote
---------------------------------------------
>Dear Panwang,

>The first thing that comes to mind is that the SOSCF converger in Firefly 8.0.1 is slightly modified. Could you try to specify

>$MCSCF OLDSTL=.T. $END

>to see if this gives you results equal to those obtained with FF 8.0.0 beta 38?
>
>
>Kind regards,
>Thom
>
>
>
>
>
>On Wed Jan 15 '14 10:32am, Panwang Zhou wrote
>---------------------------------------------
>>Dear all,

>>Recently I try to optimize excited state geometry of a molecule with State-Averaged MCSCF using the following input file:

>>!   File created by MacMolPlt 7.4.3
>>!--------- One needs extra precision -------------------
>> $MOORTH NOSTF=.T. NOZERO=.T. SYMS=.T. SYMDEN=.T. SYMVEC=.T. $END
>> $DET CVGTOL=1D-7 $END
>> $TRANS CUTTRF=1D-12 $END
>> $MCSCF ACURCY=1D-7 ENGTOL=1.0D-12 $END
>> $MCSCF NTRACK=2 $END
>>!--------------------------------------------------------
>> $CONTRL SCFTYP=MCSCF RUNTYP=OPTIMIZE EXETYP=RUN MAXIT=50 ICHARG=-1
>>    MULT=1 FSTINT=.T. GENCON=.T. INTTYP=HONDO NOSYM=1
>>    ICUT=11 ITOL=30 WIDE=.T. $END
>> $SYSTEM MWORDS=300 TIMLIM=60000.0 KDIAG=0 NOJAC=100 $END
>> $SCF DIRSCF=.T. FDIFF=.F. NCONV=8 $END
>> $P2P P2P=.T. DLB=.T. $END
>> $TRANS MPTRAN=2 DIRTRF=.T. AOINTS=DIST ALTPAR=.T. MODE=112 $END
>> $MCSCF CISTEP=ALDET FULLNR=.F. SOSCF=.T. MAXIT=100 ISTATE=2 $END
>> $DET NCORE=49 NACT=14 NELS=16 NSTATE=6 WSTATE(1)=1,1 PURES=.T. $END
>> $BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 NPFUNC=1 DIFFSP=.TRUE. $END
>> $GUESS GUESS=MOREAD NORB=359 $END
>> $STATPT OPTTOL=1D-5 NSTEP=300 HSSEND=.T. $END
>> $FORCE NVIB=2 VIBSIZ=0.005 $END
>> $DATA
>>Title
>>C1
>> C           6.0  -2.6087103932  -1.4314769433   0.0000292048
>> C           6.0  -3.9204191980  -1.0434074131  -0.0001971732
>> C           6.0  -4.2977549172   0.3624062254  -0.0003897880
>>.....
>>--- OPTIMIZED MCSCF MO-S --- GENERATED AT 11:57:37 18-JAN-2013    
>>Title                                                                          
>>E(MCSCF)=     -719.6079219077, 11 ITERS, E(NUC)=  989.8338921639
>> $VEC  
>> 1  1  2.80121665418580100D-06  1.80963473506224100D-05 -1.72772751620890100D-05  1.26171697312041000D-06 -1.05735486369750900D-09
>>................

>>The MOs are read from a previous converged SA2-MCSCF calculations with Firefly 8 Beta38.
>>Surprisingly, with Firefly 8.0.1, the following energys are obtained for the first cycle:

>>ITER    TOTAL ENERGY          DEL(E)    LAG.ASYMM.  SQCDF  MICIT   DAMP
>>   1    -719.607832495    -719.607832495  0.000021 6.846E-06  5   0.0000
>>    Warning:  state #   1 (#  1) may have been lost
>>    Warning:  state #   2 (#  6) may have been lost
>>    Warning:  remapping target state #   2 to converged CI state #   6
>>     ----------START APPROXIMATE SECOND ORDER MCSCF----------
>>   2    -719.549772183       0.058060312  0.012006 8.024E-03  1   0.0000
>>    Warning:  state #   1 (#  1) may have been lost
>>    Warning:  state #   2 (#  6) may have been lost
>>    Warning:  remapping target state #   2 to converged CI state #   6
>>   3    -719.553559929      -0.003787747  0.003057 3.419E-03  1   0.0000
>>    Warning:  state #   1 (#  1) may have been lost
>>    Warning:  state #   2 (#  6) may have been lost
>>    Warning:  remapping target state #   2 to converged CI state #   6
>>   4    -719.554053578      -0.000493649  0.001052 6.190E-04  1   0.0000
>>    Warning:  state #   1 (#  1) may have been lost
>>    Warning:  state #   2 (#  6) may have been lost
>>    Warning:  remapping target state #   2 to converged CI state #   6
>>   5    -719.554137039      -0.000083461  0.000657 5.460E-04  1   0.0000
>>    Warning:  state #   1 (#  1) may have been lost
>>    Warning:  state #   2 (#  6) may have been lost
>>    Warning:  remapping target state #   2 to converged CI state #   6
>>   6    -719.554182119      -0.000045079  0.000366 1.857E-04  1   0.0000
>>    Warning:  state #   1 (#  1) may have been lost
>>    Warning:  state #   2 (#  6) may have been lost
>>    Warning:  remapping target state #   2 to converged CI state #   6
>>   7    -719.554198750      -0.000016631  0.000233 2.111E-04  1   0.0000
>>    Warning:  state #   1 (#  1) may have been lost
>>    Warning:  state #   2 (#  6) may have been lost
>>    Warning:  remapping target state #   2 to converged CI state #   6
>>   8    -719.554209319      -0.000010569  0.000144 4.957E-05  1   0.0000
>>    Warning:  state #   1 (#  1) may have been lost
>>    Warning:  state #   2 (#  6) may have been lost
>>    Warning:  remapping target state #   2 to converged CI state #   6
>>   9    -719.554212371      -0.000003052  0.000081 1.474E-05  1   0.0000
>>    Warning:  state #   1 (#  1) may have been lost
>>    Warning:  state #   2 (#  6) may have been lost
>>    Warning:  remapping target state #   2 to converged CI state #   6
>>  10    -719.554213261      -0.000000890  0.000048 1.384E-06  1   0.0000
>>........
>>
>>and the MCSCF energy will become difficult to converge and the optimization will stop after two cycles due to MSCSCF energy convergence problems.

>>Then I swith to Firefly 8, and the following results are obtained:

>>ITER    TOTAL ENERGY          DEL(E)    LAG.ASYMM.  SQCDF  MICIT   DAMP
>>   1    -719.607832495    -719.607832495  0.000021 6.846E-06  5   0.0000
>>     ----------START APPROXIMATE SECOND ORDER MCSCF----------
>>   2    -719.607832500      -0.000000005  0.000006 6.892E-09  1   0.0000
>>   3    -719.607832501      -0.000000002  0.000002 3.929E-09  1   0.0000
>>   4    -719.607832501       0.000000000  0.000001 4.392E-10  1   0.0000
>>   5    -719.607832501       0.000000000  0.000000 4.014E-10  1   0.0000
>>   6    -719.607832501       0.000000000  0.000000 2.758E-11  1   0.0000
>>   7    -719.607832501       0.000000000  0.000000 8.581E-12  1   0.0000
>>   8    -719.607832501       0.000000000  0.000000 5.537E-13  1   0.0000

>>          --------------------
>>          LAGRANGIAN CONVERGED
>>          --------------------

>> FINAL MCSCF ENERGY IS     -719.6078325015 AFTER   8 ITERATIONS

>>This is normal because I just increase convergence precision.

>>So, what changes have been done in Firefly 8.0.1 makes this problem and which result is correct?

>>Thanks in advance.

>>Best Regards!

>>


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