From NWChem
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Posts 20
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| 4:44:19 PM PDT - Mon, Jul 28th 2014 |
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I am dealing with CCSD(T) calculation for some molecules.
For some reason, I ran with both Nwchem and Molpro codes for a molecule.
While I got so different results for the same molecule with the same geometry.
Could some one tell me the reason?
By the way, I am using molpro 2012 and nwchem 6.3.
Actually, I didn't see the difference for what I did before.
Thanks a lot.
Zongtang
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Gets Around
Threads 18
Posts 133
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| 5:50:43 PM PDT - Mon, Jul 28th 2014 |
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How badly do they diverge? Can you provide input and output files for a pair of divergent calculations? I do not have access to Molpro, but I have been in the unpleasant position of trying to harmonize an underspecified method between two different quantum chemistry packages.
Some things to consider:
-Are both packages using the exact same basis set definitions? Specify basis set definitions inline with your input file or check your basis set libraries carefully to be sure that e.g. "6-311+G*" really means what you expect in both calculations.
-Are any orbitals frozen in the calcuations? If so, are they the same orbitals? Gaussian applies orbital freezing schemes by default for post-HF calculations while NWChem does not; I don't know what Molpro does.
-Are convergence criteria sufficiently similar for both calculations? This can be a very hard question to answer a priori, as different programs specify convergence criteria in different ways and not just with different numbers. It's a question best investigated after you have eliminated more obvious culprits.
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Clicked A Few Times
Threads 7
Posts 20
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| 10:54:11 PM PDT - Mon, Jul 28th 2014 |
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Thank you so much. Actually I ran the molpro with the same size of calculation of the same molecule to check the T1 diagnostic. The convergence criterias are similar.
I worry about that because the difference is larger than 0.1 hatree.
For one of them, the HF energy is the same and the CCSD correlation energy is very different.
so either one of calculations should be wrong.
I am thinking about the reasons such as the state of the molecule or the multi-reference character of the molecule.
Would that cause the difference?
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Gets Around
Threads 18
Posts 133
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| 2:41:20 AM PDT - Tue, Jul 29th 2014 |
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I would guess that different programs become more sensitive to implementation choices under "difficult" conditions, meaning anything other than neutral closed shell systems near equilibrium geometries that are well-described by a single reference. A 0.1 hartree difference is indeed large. It is good to hear that you have at least one calculation where the HF energies are the same, because that clears up worries about basis sets, at least for that calculation. I would encourage you to look at the calculations where HF energies are the same more closely, to figure out where results begin to significantly diverge between programs. I would also wonder about calculations where the HF energies are not close. That will be a problem if you want to continue using both programs for a single line of research.
If you want to try to compare Molpro and NWChem results against a third program, Psi4 is pretty capable and well-documented: https://github.com/psi4/psi4public
I don't know if that well help resolve your puzzle or only deepen it, though.
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Edoapra Forum:Admin, Forum:Mod, bureaucrat, sysop
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| 9:52:37 AM PDT - Tue, Jul 29th 2014 |
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Zontang
Could you please post the input file you were using and the platform were you were running NWChem?
Thanks, Edo
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Threads 7
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| 12:08:23 AM PDT - Wed, Jul 30th 2014 |
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I think I found the problem for one molecule.
For the nwchem job, the RHF didn't converge. (the molpro job may be not correct either)
I got the error message in the scf step.
Here, would you please have a look to help me fix this issue ?
==================
The input :
echo
start mno4h.1ap.cs.ccsdt.ad
permanent_dir /home/****
memory stack 1000 mb heap 200 mb global 2100 mb noverify
title "hmno4.ccsdt.ad CCSD(T)/aug-cc-pVTZ(-PP)//B3LYP/cc-pVDZ(-PP)"
charge 0
geometry
symmetry c1
MN -0.080460 0.007636 0.000000
O 1.665752 0.086143 0.000000
H 2.077332 -0.793971 0.000000
O -0.557994 -0.749674 1.277449
O -0.557994 1.488591 0.000000
O -0.557994 -0.749674 -1.277449
end
basis spherical
H library aug-cc-pVDZ
O library aug-cc-pVDZ
Mn library aug-cc-pVDZ-PP #omitted here, for calculation, i put correct basis sets with ecp
end
set atomscf:z 1.0 -2 7.0
set atomscf:tags_z H O Mn
scf
vectors output mno4h.1ap.cs.ccsdt.ad.movecs
rhf
singlet
maxiter 200
end
task scf
ccsd
maxiter 60
thresh 1e-6
freeze atomic
end
task ccsd(t)
====================
erro message:
iter energy gnorm gmax time
----- ------------------- --------- --------- --------
1 -394.7142739629 1.49D+01 4.54D+00 3.1
Setting level-shift to 11.11 to force positive preconditioner
2 -402.1822934857 2.64D+00 4.43D-01 3.4
3 -402.4827505038 1.97D+00 3.83D-01 3.5
4 -402.5946928243 8.77D-01 1.48D-01 3.7
5 -402.6440042851 3.86D-01 6.85D-02 3.8
6 -402.6667435139 2.21D-01 6.35D-02 4.2
7 -402.6701957197 2.12D-02 6.03D-03 4.4
ga_iter_lsolve: convergence stagnant ... aborting solve
8 -************** 3.90D-02 1.07D-02 5.2
9 -402.6712445617 1.51D-03 5.10D-04 5.7
ga_iter_lsolve: convergence stagnant ... aborting solve
Disabled NR: increased maxiter to 210
10 -402.6712449429 2.11D-03 8.37D-04 5.8
11 -402.6712461508 2.14D-03 6.32D-04 5.9
12 -************** 2.69D-03 8.66D-04 6.0
13 -402.6712475049 2.32D-03 6.75D-04 6.1
14 -402.6712480031 1.89D-03 3.77D-04 6.2
15 -402.6712482699 1.31D-03 3.43D-04 6.3
16 -402.6712484015 1.08D-03 2.57D-04 6.4
17 -************** 7.35D-04 1.74D-04 6.5
18 -402.6712485453 5.92D-04 1.23D-04 6.5
19 -402.6712485693 5.14D-04 1.20D-04 6.6
20 -402.6712485929 4.52D-04 1.04D-04 6.7
21 -402.6712486132 4.36D-04 9.50D-05 6.7
22 -402.6712486325 4.75D-04 1.38D-04 6.8
23 -402.6712486526 4.77D-04 1.04D-04 6.8
24 -402.6712486689 3.00D-04 1.07D-04 6.9
25 -402.6712486808 2.89D-04 9.44D-05 7.0
26 -402.6712486864 2.14D-04 5.86D-05 7.1
27 -402.6712486913 1.68D-04 4.05D-05 7.2
28 -402.6712486938 1.39D-04 3.12D-05 7.3
29 -402.6712486953 1.33D-04 3.44D-05 7.4
30 -402.6712486972 9.62D-05 1.85D-05 7.5
============
I tried to play around to get rid of symmetry or increase the iteration steps, or set atomscf, et al, the problem was still there.
Thanks a lot.
Zongtang
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Edited On 12:10:23 AM PDT - Wed, Jul 30th 2014 by Zfang
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Edoapra Forum:Admin, Forum:Mod, bureaucrat, sysop
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Threads 7
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| 10:37:27 AM PDT - Wed, Jul 30th 2014 |
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basis set
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Zongtang
Could you please report the basis set you are using? The following is not very useful.
Mn library aug-cc-pVDZ-PP #omitted here, for calculation, i put correct basis sets with ecp
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Clicked A Few Times
Threads 7
Posts 20
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| 11:10:20 AM PDT - Wed, Jul 30th 2014 |
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ok, sure
the mn basis set I am using as
- cc-pVDZ-PP
Mn s
2080.37 0.000159
304.649 0.000994
22.2505 0.051511
7.56933 -0.393048
1.56197 0.740590
0.654311 0.457874
0.107776 0.016591
0.039409 -0.002586
Mn s
2080.37 -0.000038
304.649 -0.000277
22.2505 -0.012210
7.56933 0.101296
1.56197 -0.238569
0.654311 -0.258056
0.107776 0.577934
0.039409 0.565458
Mn s
2080.37 0.000099
304.649 0.000494
22.2505 0.030238
7.56933 -0.242022
1.56197 0.945993
0.654311 -0.407703
0.107776 -1.658454
0.039409 1.634148
Mn s
0.039409 1.0
Mn p
54.1365 0.003585
11.5345 -0.068823
2.91993 0.345476
1.31207 0.506638
0.565154 0.262497
0.153142 0.021029
0.048714 -0.002835
Mn p
54.1365 -0.000772
11.5345 0.016640
2.91993 -0.096406
1.31207 -0.166698
0.565154 -0.014675
0.153142 0.545351
0.048714 0.564209
Mn p
54.1365 -0.000978
11.5345 0.021319
2.91993 -0.121381
1.31207 -0.222495
0.565154 -0.016634
0.153142 0.799219
0.048714 0.296449
Mn p
0.048714 1.0
Mn d
34.4465 0.021926
10.7969 0.112236
3.83655 0.293563
1.39838 0.427063
0.476480 0.377381
0.138120 0.145135
Mn d
34.4465 -0.022540
10.7969 -0.118668
3.83655 -0.309567
1.39838 -0.302288
0.476480 0.306841
0.138120 0.714822
Mn d
0.138120 1.0
Mn f
1.3394 1.0
- aug-cc-pVDZ-PP
Mn s
0.0144 1.0
Mn p
0.0155 1.0
Mn d
0.0400 1.0
Mn f
0.3976 1.0
end
ecp
Mn nelec 10
Mn S
2 19.77859586351460 208.36277759981999
2 8.36429231183498 40.67136312517160
Mn P
2 19.75517256031370 42.82221279051267
2 19.58138625787880 74.14325787868533
2 8.09003570055466 8.57859438555583
2 8.31459920850757 20.38995721451193
Mn D
2 24.19571159002280 -9.37867882820444
2 24.53647306721080 -14.14683917959722
2 7.95149778468298 -0.29670061844163
2 7.93161326885935 -0.44295145020000
Mn F
2 12.19160291115040 -2.56699301425514
2 14.77200557195830 -5.28909520512491
end
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Edoapra Forum:Admin, Forum:Mod, bureaucrat, sysop
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Threads 7
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| 11:25:23 AM PDT - Wed, Jul 30th 2014 |
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Zongtang
Here is the input that will give you a converged SCF by first using the DIIS convergence out of the DFT module
echo
start mno4h.1ap.cs.ccsdt.ad
permanent_dir /home/****
memory stack 1000 mb heap 200 mb global 2100 mb noverify
title "hmno4.ccsdt.ad CCSD(T)/aug-cc-pVTZ(-PP)//B3LYP/cc-pVDZ(-PP)"
charge 0
geometry
symmetry c1
MN -0.080460 0.007636 0.000000
O 1.665752 0.086143 0.000000
H 2.077332 -0.793971 0.000000
O -0.557994 -0.749674 1.277449
O -0.557994 1.488591 0.000000
O -0.557994 -0.749674 -1.277449
end
basis spherical
H library aug-cc-pVDZ
O library aug-cc-pVDZ
# cc-pVDZ-PP
Mn s
2080.37 0.000159
304.649 0.000994
22.2505 0.051511
7.56933 -0.393048
1.56197 0.740590
0.654311 0.457874
0.107776 0.016591
0.039409 -0.002586
Mn s
2080.37 -0.000038
304.649 -0.000277
22.2505 -0.012210
7.56933 0.101296
1.56197 -0.238569
0.654311 -0.258056
0.107776 0.577934
0.039409 0.565458
Mn s
2080.37 0.000099
304.649 0.000494
22.2505 0.030238
7.56933 -0.242022
1.56197 0.945993
0.654311 -0.407703
0.107776 -1.658454
0.039409 1.634148
Mn s
0.039409 1.0
Mn p
54.1365 0.003585
11.5345 -0.068823
2.91993 0.345476
1.31207 0.506638
0.565154 0.262497
0.153142 0.021029
0.048714 -0.002835
Mn p
54.1365 -0.000772
11.5345 0.016640
2.91993 -0.096406
1.31207 -0.166698
0.565154 -0.014675
0.153142 0.545351
0.048714 0.564209
Mn p
54.1365 -0.000978
11.5345 0.021319
2.91993 -0.121381
1.31207 -0.222495
0.565154 -0.016634
0.153142 0.799219
0.048714 0.296449
Mn p
0.048714 1.0
Mn d
34.4465 0.021926
10.7969 0.112236
3.83655 0.293563
1.39838 0.427063
0.476480 0.377381
0.138120 0.145135
Mn d
34.4465 -0.022540
10.7969 -0.118668
3.83655 -0.309567
1.39838 -0.302288
0.476480 0.306841
0.138120 0.714822
Mn d
0.138120 1.0
Mn f
1.3394 1.0
# aug-cc-pVDZ-PP
Mn s
0.0144 1.0
Mn p
0.0155 1.0
Mn d
0.0400 1.0
Mn f
0.3976 1.0
end
ecp
Mn nelec 10
Mn S
2 19.77859586351460 208.36277759981999
2 8.36429231183498 40.67136312517160
Mn P
2 19.75517256031370 42.82221279051267
2 19.58138625787880 74.14325787868533
2 8.09003570055466 8.57859438555583
2 8.31459920850757 20.38995721451193
Mn D
2 24.19571159002280 -9.37867882820444
2 24.53647306721080 -14.14683917959722
2 7.95149778468298 -0.29670061844163
2 7.93161326885935 -0.44295145020000
Mn F
2 12.19160291115040 -2.56699301425514
2 14.77200557195830 -5.28909520512491
end
dft
xc hfexch
convergence energy 1d-10
tolerances acccoul 12
vectors input atomic output dft.mos
maxiter 45
end
set quickguess t
task dft ignore
scf
tol2e 1d-12
vectors input dft.mos output hf.mos
end
ccsd
maxiter 60
thresh 1e-6
freeze atomic
end
task ccsd(t)
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Clicked A Few Times
Threads 7
Posts 20
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| 2:08:48 PM PDT - Thu, Jul 31st 2014 |
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Finally we found out the issue.
For our CCSD(T) calculations with ECP basis sets for metal with NWChem, the default "Freeze atomic" didn't give right number of core orbitals. This would cause the huge difference of ccsd(t) number.
Also a couple of linear dependencies were removed due to the default threshold making the different HF value. I tried tight threshold and fixed that problem.
Thanks for all your guys' responses.
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