[molpro-user] MCSCF Energy Varies When Printing CI Coefficient from natorb
Toru Shiozaki
shiozaki at theochem.uni-stuttgart.de
Wed Aug 31 22:42:20 BST 2011
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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