[molpro-user] MCSCF Energy Varies When Printing CI Coefficient from natorb

Mingyang Chen mchen10 at crimson.ua.edu
Wed Aug 31 23:14:20 BST 2011


Dear Toru
thanks a lot
mingyang

On Wed, Aug 31, 2011 at 4:42 PM, Toru Shiozaki
<shiozaki at theochem.uni-stuttgart.de> wrote:
> Dear Mingyang,
>
> this is a known problem, reported in the bug list some time ago (but 2990), and we are sorry that you've hit it.
>
> Molpro's MCSCF performs one additional internal CI when you request to print CI coefficients.
> But this additional internal CI sometimes converges to a wrong state.
>
> For the time being, perhaps you could try to use a larger pspace threshold; for instance
>
>>> {multi;occ,9,3,3,2,6,3,3,1;closed,3,2,2,0,3,1,1,0;pspace,1.0;wf,51,8,7;natorb,ci,print}
>
> I have implemented some codes for this problem in developer's version (but only with config card & CASSCF so far);
> I hope that we could include them it in the next release, but not sure.
>
> Best wishes,
> Toru
>
> On Aug 31, 2011, at 10:21 PM, Mingyang Chen wrote:
>
>> Dear everyone,
>>
>> I tried to print out the CI coefficients when doing some MCSCF
>> calculations for Ir3 (linear, DeltaU in Dinfh -> Au or B1u in D2h) .
>> The B1u and Au states are degenerate, with the same total energy. The
>> B1u state calculation gives the same energy from MCSCF and "ci,natorb"
>> and the CI coefficient looks reasonable, but the Au state calculation
>> gives a much higher total energy in the natorb section than in the
>> MCSCF. Is there something wrong in my Au state calculation?
>>
>> thanks
>> Mingyang
>>
>>
>> Input for Au (in D2h symm) state:
>>
>> ***
>> ! geometry setting ...
>> ! basis set setting ...
>> {hf;wf,51,8,7}    ! Au ! {hf;wf,51,5,7} for B1u
>> {multi;occ,9,3,3,2,6,3,3,1;closed,3,2,2,0,3,1,1,0;wf,51,8,7;natorb,ci,print}
>>  ! {multi;occ,9,3,3,2,6,3,3,1;closed,3,2,2,0,3,1,1,0;wf,51,5,7;natorb,ci,print}
>> for B1u
>> ---
>>
>>
>> Output (Au) gives:
>>
>> ...
>> Convergence thresholds  0.10E-01 (gradient)  0.10E-05 (energy)
>> 0.10E-02 (step length)
>>
>> Number of orbital rotations:    1092     (  35 Core/Active  435
>> Core/Virtual   0 Active/Active  622 Active/Virtual)
>> Total number of variables:     99650
>>
>>
>> ITER. MIC  NCI  NEG     ENERGY(VAR)     ENERGY(PROJ)   ENERGY CHANGE
>>   GRAD(0)  GRAD(ORB)   GRAD(CI)     STEP       TIME
>>
>>   1   57   64    0    -310.91677097    -310.92038127   -0.00361030
>> 0.10411834 0.00000006 0.00361763  0.61D-01     85.67
>>   2   36   67    0    -310.92039193    -310.92040002   -0.00000809
>> 0.00324527 0.00000000 0.00437243  0.38D-02    177.26
>>   3   36   67    0    -310.92040193    -310.92040476   -0.00000283
>> 0.00124437 0.00000000 0.00312089  0.20D-02    268.79
>>   4   36   67    0    -310.92040576    -310.92040693   -0.00000117
>> 0.00089611 0.00000000 0.00636783  0.12D-02    360.15
>>   5   32   67    0    -310.92933929    -310.93280459   -0.00346531
>> 0.10885064 0.00000000 0.02473198  0.60D-01    451.34
>>   6   26   61    0    -310.93283721    -310.93284263   -0.00000542
>> 0.00321968 0.00000002 0.00109470  0.31D-02    534.92
>>   7   25   39    0    -310.93284267    -310.93284268   -0.00000001
>> 0.00017197 0.00000000 0.00036978  0.11D-03    586.03
>>
>> ** WVFN ****  CONVERGENCE REACHED, FINAL GRADIENT:  0.40D-04
>>
>>
>> First order charge density matrix for state 1.8 saved on record
>> 2141.2 (density set 1)
>>
>> Results for state 1.8
>> =====================
>>
>> !MCSCF STATE 1.8 ENERGY             -310.932842681318
>> Nuclear energy                       153.91119120
>> Kinetic energy                       105.80948255
>> One electron energy                 -850.76803328
>> Two electron energy                  385.92399940
>> Virial ratio                           3.93861037
>> ...
>>
>> CI vector
>> =========
>>
>> 222aa0 2 2 aa 2a2 2a 2a 2      0.5749872
>> a22aa0 2 2 a2 222 2a 2a a      0.3347404
>> 222a20 2 2 2a 2aa 2a 2a a     -0.2453940
>> 2222a0 a a 2a 2a2 2a 2a 2     -0.2267273
>> 222aa0 a 2 2a 2a2 22 2a a     -0.1867435
>> 222aa0 2 a 2a 2a2 2a 22 a     -0.1867435
>> a22220 2 2 a2 2aa 2a 2a a     -0.1371137
>> a222a0 a a 22 222 2a 2a a     -0.1367465
>> 222aa0 a 2 2a 222 2a aa 2     -0.1125500
>> 222aa0 2 a 2a 222 aa 2a 2     -0.1125500
>> 22aa20 a 2 2a 2a2 22 2a a     -0.1100730
>> 22aa20 2 a 2a 2a2 2a 22 a     -0.1100730
>> 22aa20 2 2 aa 2a2 a2 2a 2     -0.1071175
>> 22aa20 2 2 aa 2a2 2a a2 2      0.1071175
>> a222a0 a 2 a2 2a2 22 2a a     -0.1054133
>> a222a0 2 a a2 2a2 2a 22 a     -0.1054133
>> 22aa20 2 2 aa 2a2 2a 2a 2      0.0846196
>> 222aa0 2 2 aa 2a2 a2 a2 2      0.0787271
>> 22a220 a a 2a 2a2 2a 2a 2      0.0663686
>> a22aa0 2 2 2a 222 2a 2a a      0.0660027
>> a222a0 a 2 a2 222 2a aa 2     -0.0657291
>> a222a0 2 a a2 222 aa 2a 2     -0.0657291
>> a2a220 a 2 a2 2a2 22 2a a      0.0650328
>> a2a220 2 a a2 2a2 2a 22 a      0.0650328
>> a2aa20 2 2 a2 222 2a a2 a      0.0637471
>> a2aa20 2 2 a2 222 a2 2a a     -0.0637471
>> a2aa20 2 2 a2 222 2a 2a a      0.0549058
>> 222aa0 a 2 2a 222 a2 aa 2      0.0529908
>> 222aa0 2 a 2a 222 aa a2 2     -0.0529908
>> 22a220 a a 2a 2a2 2a a2 2      0.0508929
>> 22a220 a a 2a 2a2 a2 2a 2     -0.0508929
>> 222a20 2 2 2a 2aa a2 2a a     -0.0508158
>> 222a20 2 2 2a 2aa 2a a2 a      0.0508158
>>
>> TOTAL ENERGIES                      -310.91677189
>>
>>
>>
>>
>>
>>
>> -----------------------------------------------------------------------------------------------------------------------------------------------------------------
>>
>> compared with the B1u output:
>>
>>
>> ...
>>
>>
>> Results for state 1.5
>> =====================
>>
>> !MCSCF STATE 1.5 ENERGY             -310.932842682065
>> Nuclear energy                       153.91123472
>> Kinetic energy                       105.80932742
>> One electron energy                 -850.76792634
>> Two electron energy                  385.92384894
>> Virial ratio                           3.93861468
>>
>> ...
>>
>> CI vector
>> =========
>>
>> 222aa0 2 2 22 2aa 2a 2a a      0.6113264
>> 22aaa0 2 2 2a 22a 2a 2a 2     -0.6099084
>> 2aaaa0 a 2 2a 222 22 2a 2     -0.1226944
>> 2aaaa0 2 a 2a 222 2a 22 2      0.1226944
>> 2a2aa0 a 2 22 2a2 22 2a a     -0.1198499
>> 2a2aa0 2 a 22 2a2 2a 22 a      0.1198499
>> 2a22a0 2 2 22 2aa a2 2a a      0.1027613
>> 2a22a0 2 2 22 2aa 2a a2 a      0.1027613
>> 2aa2a0 2 2 2a 22a a2 2a 2      0.1013039
>> 2aa2a0 2 2 2a 22a 2a a2 2      0.1013039
>> 222aa0 2 2 22 2aa a2 a2 a     -0.0655333
>> 22aaa0 2 2 2a 22a a2 a2 2      0.0654110
>> 222aa0 a a 22 2aa 22 22 a     -0.0559471
>> 22aaa0 a a 2a 22a 22 22 2      0.0545224
>> 22a0aa 2 2 2a a22 2a 2a 2      0.0540423
>> 2220aa 2 2 22 aa2 2a 2a a      0.0540154
>> 22aaa2 2 2 2a 02a 2a 2a 2      0.0522067
>> 222aa2 2 2 22 0aa 2a 2a a     -0.0519294
>> 22aaaa a 2 2a b2a 22 2a 2     -0.0511957
>> 22aaaa 2 a 2a b2a 2a 22 2      0.0511957
>> 222aaa a 2 22 baa 22 2a a     -0.0509685
>> 222aaa 2 a 22 baa 2a 22 a      0.0509685
>> 222aa0 a 2 2a 22a 2a 22 a      0.0502617
>> 222aa0 2 a 2a 22a 22 2a a      0.0502617
>>
>> TOTAL ENERGIES                      -310.93284268
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