I think I know one problem in the creation of the wfn file in TM 6.3.1 when using ricc2.
Due to the perturbation the occupation of an orbital can become larger than 2 and also negative but Turbomole seems only to exports the orbitals with occupation > 0.10E-11 and therefore the orbitals with negative occupation are missing in the wfn file. I don't know if one should count orbitals with a negative occupation number as occupied in the output (this seems to me to be more a philosophical question) . In any case, I think they are important as they for example have an effect on the number of electrons calculated as sum over all occupation numbers.
This can easily be reproduced when for example calculation H
2O with aug-cc-pVDZ basis set.
Analysis of the density matrix:
Number of occupied orbitals (occupation > 0.10E-11): 38
Number of unoccupied orbitals (occupation <= 0.10E-11): 5
total number of electrons as calculated from occupation numbers: 10.0000000000
Occupation numbers:
2.000002 1.985848 1.968297 1.966035 1.965894
0.024128 0.022744 0.020641 0.011503 0.006185
0.006132 0.005912 0.005255 0.005223 0.000975
0.000867 0.000662 0.000661 0.000571 0.000557
0.000525 0.000451 0.000288 0.000286 0.000272
0.000210 0.000133 0.000068 0.000051 0.000026
0.000025 0.000024 0.000021 0.000018 0.000010
0.000009 0.000001 0.000000 0.000000 0.000000
-0.000002 -0.000103 -0.000405
And the corresponding lines in the wfn file are
NO 1 NO 0.0 OCC NO = 2.0000019 ORB. ENERGY = 0.0000000
NO 2 NO 0.0 OCC NO = 1.9858482 ORB. ENERGY = 0.0000000
NO 3 NO 0.0 OCC NO = 1.9682972 ORB. ENERGY = 0.0000000
NO 4 NO 0.0 OCC NO = 1.9660346 ORB. ENERGY = 0.0000000
NO 5 NO 0.0 OCC NO = 1.9658936 ORB. ENERGY = 0.0000000
NO 6 NO 0.0 OCC NO = 0.0241280 ORB. ENERGY = 0.0000000
NO 7 NO 0.0 OCC NO = 0.0227437 ORB. ENERGY = 0.0000000
NO 8 NO 0.0 OCC NO = 0.0206414 ORB. ENERGY = 0.0000000
NO 9 NO 0.0 OCC NO = 0.0115034 ORB. ENERGY = 0.0000000
NO 10 NO 0.0 OCC NO = 0.0061848 ORB. ENERGY = 0.0000000
NO 11 NO 0.0 OCC NO = 0.0061317 ORB. ENERGY = 0.0000000
NO 12 NO 0.0 OCC NO = 0.0059125 ORB. ENERGY = 0.0000000
NO 13 NO 0.0 OCC NO = 0.0052547 ORB. ENERGY = 0.0000000
NO 14 NO 0.0 OCC NO = 0.0052232 ORB. ENERGY = 0.0000000
NO 15 NO 0.0 OCC NO = 0.0009751 ORB. ENERGY = 0.0000000
NO 16 NO 0.0 OCC NO = 0.0008673 ORB. ENERGY = 0.0000000
NO 17 NO 0.0 OCC NO = 0.0006625 ORB. ENERGY = 0.0000000
NO 18 NO 0.0 OCC NO = 0.0006606 ORB. ENERGY = 0.0000000
NO 19 NO 0.0 OCC NO = 0.0005712 ORB. ENERGY = 0.0000000
NO 20 NO 0.0 OCC NO = 0.0005569 ORB. ENERGY = 0.0000000
NO 21 NO 0.0 OCC NO = 0.0005253 ORB. ENERGY = 0.0000000
NO 22 NO 0.0 OCC NO = 0.0004514 ORB. ENERGY = 0.0000000
NO 23 NO 0.0 OCC NO = 0.0002878 ORB. ENERGY = 0.0000000
NO 24 NO 0.0 OCC NO = 0.0002861 ORB. ENERGY = 0.0000000
NO 25 NO 0.0 OCC NO = 0.0002719 ORB. ENERGY = 0.0000000
NO 26 NO 0.0 OCC NO = 0.0002099 ORB. ENERGY = 0.0000000
NO 27 NO 0.0 OCC NO = 0.0001335 ORB. ENERGY = 0.0000000
NO 28 NO 0.0 OCC NO = 0.0000679 ORB. ENERGY = 0.0000000
NO 29 NO 0.0 OCC NO = 0.0000507 ORB. ENERGY = 0.0000000
NO 30 NO 0.0 OCC NO = 0.0000257 ORB. ENERGY = 0.0000000
NO 31 NO 0.0 OCC NO = 0.0000247 ORB. ENERGY = 0.0000000
NO 32 NO 0.0 OCC NO = 0.0000241 ORB. ENERGY = 0.0000000
NO 33 NO 0.0 OCC NO = 0.0000212 ORB. ENERGY = 0.0000000
NO 34 NO 0.0 OCC NO = 0.0000177 ORB. ENERGY = 0.0000000
NO 35 NO 0.0 OCC NO = 0.0000096 ORB. ENERGY = 0.0000000
NO 36 NO 0.0 OCC NO = 0.0000090 ORB. ENERGY = 0.0000000
NO 37 NO 0.0 OCC NO = 0.0000012 ORB. ENERGY = 0.0000000
NO 38 NO 0.0 OCC NO = 0.0000001 ORB. ENERGY = 0.0000000
As the negative entries are missing the sum over all OCC NO in the wfn-file is 10.0005103 and not longer 10.0000000000 as it should be.
I (naively) think that this issue could easily be fixed (one just has to look on the absolute value of the occupation number before deciding if this orbital is exported).
If one is already in this part of the code one can maybe also allow the output (in TM itself and in the wfn file) to have orbital numbers with more than 3 digits. This is not uncommon in these days and then I would have recognized this bug more easily.
(I don't know about the moden format but when running t2molden I seem to get 40 Orbitals of which 4 (!) have an "Occup= 2.000000" and all other 36 have "Occup= 0.000000". I don't know if this can be right.)
But besides this post-HF issue I also have huge troubles with creating proper wfn-files even for DFT/HF-cases (where all occ numbers are positive)
- For some molecules I get the error "too many iterations in tqli (rdiag)" and no wfn is created at all. This problem was already posted here.
- Sometimes the created wfn-file contains huge/small numbers (see attached example) or even NaN entries as coefficients,
- Sometimes the wfn-file looks OK but (AIMAll complains that) it's not proper normalized
The problem with these issues is that I already spent more than a week in trying to reproducible get the error (I already tried different computer clusters, different types of parallelisation, older version of tM...). Sometimes the same input work and sometimes it does not. Also sometimes it worked for me if I just use ridft/dscf -proper to overwrite the faulty wfn file with a correct (proper ;-) ) one.
Can somebody comment on this negative occ. values and maybe also has an idea about the other problems? I really like QTAIM and would love to do it more often.
Is there a general guide line what questions/comments one should e-mail to the support and for which this forum is the right place? I was expecting that the support guys are also reading this forum as the number of total posts/day is still reasonable.