[CP2K:10302] Re: MO coefficients not normalized?
Krack Matthias (PSI)
matthia... at psi.ch
Fri May 11 12:32:08 UTC 2018
Hi Daniel
did you check if other basis sets like DZVP-MOLOPT-SR cause the same behaviour?
Best regards
Matthias
From: cp... at googlegroups.com [mailto:cp... at googlegroups.com] On Behalf Of Dan_M
Sent: 11 May 2018 11:48
To: cp2k
Subject: Re: [CP2K:10302] Re: MO coefficients not normalized?
Hi Matthias,
I did what you suggested and even though it seemed to make the convergence a bit smoother for OT, still it does not improve the diagonalization.
Specifically, I set EPS_DEFAULT 1.0E-14 and dropped the *_CUTOFF and XC smoothing, and converged with OT and EPS_SCF 1.0E-8.
With this optimized wfn I started the diagonalization (algorithm standard, direct_p_mixing, alpha 0.1) and doesn't work:
Step Update method Time Convergence Total energy Change
------------------------------------------------------------------------------
1 P_Mix/Diag. 0.10E+00 5.9 1.04345518 -2483.7051317469 -2.48E+03
2 P_Mix/Diag. 0.10E+00 6.2 0.21526298 -2483.6950681260 1.01E-02
3 P_Mix/Diag. 0.10E+00 6.3 0.18583657 -2483.6983718168 -3.30E-03
4 P_Mix/Diag. 0.10E+00 6.2 0.15912799 -2483.7005021331 -2.13E-03
5 P_Mix/Diag. 0.10E+00 6.6 0.13537782 -2483.7018913141 -1.39E-03
6 P_Mix/Diag. 0.10E+00 7.2 0.11457317 -2483.7028012278 -9.10E-04
7 P_Mix/Diag. 0.10E+00 6.2 0.09655329 -2483.7033951772 -5.94E-04
8 P_Mix/Diag. 0.10E+00 6.2 0.08107945 -2483.7037777217 -3.83E-04
9 P_Mix/Diag. 0.10E+00 6.4 0.06788010 -2483.7040173663 -2.40E-04
10 P_Mix/Diag. 0.10E+00 6.2 1.05830128 -2483.7041598673 -1.43E-04
11 P_Mix/Diag. 0.10E+00 6.4 0.27282434 -2483.6885022250 1.57E-02
12 P_Mix/Diag. 0.10E+00 6.2 0.19477670 -2483.6934564774 -4.95E-03
13 P_Mix/Diag. 0.10E+00 6.3 0.15900657 -2483.6966522751 -3.20E-03
14 P_Mix/Diag. 0.10E+00 6.3 0.13501187 -2483.6987689554 -2.12E-03
15 P_Mix/Diag. 0.10E+00 6.2 0.11406673 -2483.7002037460 -1.43E-03
16 P_Mix/Diag. 0.10E+00 6.3 0.09597285 -2483.7011950370 -9.91E-04
17 P_Mix/Diag. 0.10E+00 6.3 0.08046688 -2483.7018901542 -6.95E-04
18 P_Mix/Diag. 0.10E+00 6.3 0.06782297 -2483.7023829252 -4.93E-04
19 P_Mix/Diag. 0.10E+00 6.3 1.04290747 -2483.7027348383 -3.52E-04
20 P_Mix/Diag. 0.10E+00 6.2 0.21550410 -2483.6899786616 1.28E-02
21 P_Mix/Diag. 0.10E+00 6.2 0.18544263 -2483.6942956542 -4.32E-03
....
BTW, that was after I set EPS_DIIS in &SCF below EPS_SCF, since otherwise things get much worse after DIIS starts:
Step Update method Time Convergence Total energy Change
------------------------------------------------------------------------------
1 P_Mix/Diag. 0.10E+00 5.9 1.04345518 -2483.7051317469 -2.48E+03
2 P_Mix/Diag. 0.10E+00 6.5 0.21526298 -2483.6950681260 1.01E-02
3 P_Mix/Diag. 0.10E+00 6.5 0.18583657 -2483.6983718168 -3.30E-03
4 P_Mix/Diag. 0.10E+00 6.6 0.15912799 -2483.7005021331 -2.13E-03
5 P_Mix/Diag. 0.10E+00 6.5 0.13537782 -2483.7018913141 -1.39E-03
6 P_Mix/Diag. 0.10E+00 6.5 0.11457317 -2483.7028012278 -9.10E-04
7 P_Mix/Diag. 0.10E+00 6.5 0.09655329 -2483.7033951772 -5.94E-04
8 DIIS/Diag. 0.26E-02 6.6 1.09993086 -2483.7037777217 -3.83E-04
9 P_Mix/Diag. 0.10E+00 6.5 98.45213358 -2482.2918306873 1.41E+00
10 P_Mix/Diag. 0.10E+00 6.5 88.61338472 -2479.1562224901 3.14E+00
11 P_Mix/Diag. 0.10E+00 6.4 738.84827806 -2413.5998990757 6.56E+01
12 P_Mix/Diag. 0.10E+00 6.5 726.38204744 -2239.0573891721 1.75E+02
...
So probably you are right, there may be something else wrong. The possible issue that comes to my mind is that the system is not that simple. It is a water slab periodic in 2 dimensions and with a ~12 angstroms spacing in the 3rd dimension, treated as fully periodic (e.g. &Poisson periodic XYZ) but I made sure that the net dipole is very small and slab-slab interactions are negligible for the neutral water slab. Then there is a proton placed close to a water in the slab surface, geometry very far from optimal (some could say "unphysical" but it should be treatable --and actually it works with OT--, H+ is 1.14 angstrom away from the closest O and 1.47 to the closest H). I am aware that of course I can not expect to converge the wfn for any kind of crazy geometry, but what I don't understand is why if OT converges (despite all the issues like charged cell, exotic geometry, etc) then diagonalization does not. Is it possible that simply the difficult geometry screws up that much the diagonalization of the OT converged wfn?
Thanks a lot for your comments,
Daniel
El jueves, 10 de mayo de 2018, 18:43:47 (UTC+2), Matthias Krack escribió:
Hi Daniel
If your preceding OT run converged properly (tightly), the restart with diagonalisation should converge immediately or after a few steps, otherwise something is wrong.
There are some issues in your input which I would change without claiming that this will solve your problem. I would
1) use a smaller EPS_DEFAULT, e.g. at least 1.0E-12 (smaller is also fine), 1.0E-10 is not tight enough
2) drop the *_CUTOFF values in the &XC section unless you have a good reason to set some of these values explicitly
3) drop the smoothing unless you have any good reason to use it (e.g. with BLYP), since you are using with 700Ry a rather high cutoff anyway
4) use diagonalisation with direct_p_mixing and a mixing alpha of about 0.1 for restart, if that does not converge immediately or at least within a few SCF steps starting from a converged OT run, then most likely something else is wrong and it is unlikely that any other mixing method will work better and solve the problem
I understood that you are dealing with a condensed phase system. If yes, did you check that the QZV3P basis sets you are using are suited for that setup?
Best regards
Matthias
From: cp... at googlegroups.com<javascript:> [mailto:cp... at googlegroups.com<javascript:>] On Behalf Of Dan_M
Sent: 10 May 2018 18:04
To: cp2k
Subject: Re: [CP2K:10300] Re: MO coefficients not normalized?
Hi Matthias,
yest I did but it does not converge, for instance this is what I get when using Davidson diagonalization (defaults parameters for &MIXING):
Step Update method Time Convergence Total energy Change
------------------------------------------------------------------------------
1 P_Mix/Dav. 0.40E+00 8.1 0.00309369 -2483.1531852407 -2.48E+03
2 P_Mix/Dav. 0.40E+00 2.5 0.15334223 -2483.1531847710 4.70E-07
3 P_Mix/Dav. 0.40E+00 2.4 0.14839060 -2483.1496260655 3.56E-03
4 P_Mix/Dav. 0.40E+00 2.4 0.06204907 -2483.1516643558 -2.04E-03
5 P_Mix/Dav. 0.40E+00 2.4 0.72149356 -2483.1519086893 -2.44E-04
6 P_Mix/Dav. 0.40E+00 2.4 0.44697821 -2483.0750573108 7.69E-02
7 P_Mix/Dav. 0.40E+00 2.4 0.21458187 -2483.1176203039 -4.26E-02
8 P_Mix/Dav. 0.40E+00 2.4 0.09370387 -2483.1338242392 -1.62E-02
9 P_Mix/Dav. 0.40E+00 2.4 1.08948074 -2483.1415463487 -7.72E-03
10 P_Mix/Dav. 0.40E+00 2.4 0.67563179 -2482.9378947719 2.04E-01
11 P_Mix/Dav. 0.40E+00 2.4 0.32819448 -2483.0539735944 -1.16E-01
12 P_Mix/Dav. 0.40E+00 2.4 0.15275080 -2483.0996929120 -4.57E-02
13 P_Mix/Dav. 0.40E+00 2.4 1.06118539 -2483.1220162257 -2.23E-02
14 P_Mix/Dav. 0.40E+00 2.4 0.77108692 -2482.9213332983 2.01E-01
15 P_Mix/Dav. 0.40E+00 2.4 0.32374229 -2483.0459012328 -1.25E-01
16 P_Mix/Dav. 0.40E+00 2.4 0.16259590 -2483.0951505330 -4.92E-02
17 P_Mix/Dav. 0.40E+00 2.3 0.10138969 -2483.1193594430 -2.42E-02
18 P_Mix/Dav. 0.40E+00 2.4 0.06424836 -2483.1326526033 -1.33E-02
19 P_Mix/Dav. 0.40E+00 2.4 0.03960077 -2483.1403233567 -7.67E-03
...
Similar behavior happens with the other diagonalization flavors, I am playing around with the mixing parameters but no success so far.
In passing there is a curious thing I observed with OT: the wfn is converged and the eigenvalues are printed in the PDOS but they are not printed correctly together with the MO coefficients (I request eigenvalues, eigenvectors and occupations), instead I get:
MO EIGENVALUES, MO OCCUPATION NUMBERS, AND SPHERICAL MO EIGENVECTORS
1 2 3 4
0.000000 0.000000 0.000000 0.000000
2.000000 2.000000 2.000000 2.000000
1 1 H 1s 0.041699 -0.021600 0.017105 0.034420
2 1 H 2s -0.001594 0.001644 -0.000409 -0.000568
3 1 H 3s -0.011532 0.007340 -0.005061 -0.008943
4 1 H 4s -0.005753 0.006757 -0.005764 -0.009668
...
For what it is worth, I am using version 5.1 (svn 18091) and the relevant parts of the electronic structure are these (for the diagonalization I just turn &OT F and uncomment the relevant parts; also I tried with and without ADDED_MOS/NLUMO etc etc...)
&FORCE_EVAL
METHOD QS
&DFT
CHARGE 1
BASIS_SET_FILE_NAME ./GTH_BASIS_SETS
POTENTIAL_FILE_NAME ./GTH_POTENTIALS
&PRINT
&MULLIKEN ON
&EACH
JUST_ENERGY 1
&END EACH
&END
&HIRSHFELD
&EACH
JUST_ENERGY 1
&END EACH
&END
&MO_CUBES
WRITE_CUBE F
! NLUMO 576
&END
&MO ON
&EACH
JUST_ENERGY 1
QS_SCF 0
&END
! MO_INDEX_RANGE 1 1152
EIGENVALUES
EIGENVECTORS
OCCUPATION_NUMBERS
&END
&PDOS
&EACH
JUST_ENERGY 1
&END
APPEND
! NLUMO 576
&END
! &AO_MATRICES ON
! OVERLAP T
! &END
&END
&MGRID
REL_CUTOFF 70.0
NGRIDS 5
CUTOFF 700.0
&END MGRID
&QS
METHOD GPW
EPS_DEFAULT 1.0E-10
MAP_CONSISTENT
&END QS
&SCF
&PRINT
&RESTART
BACKUP_COPIES 1
&END RESTART
&END PRINT
SCF_GUESS RESTART
! ADDED_MOS 576
MAX_SCF 20
EPS_SCF 2.0E-7
! EPS_LUMO 2.0E-7
! MAX_ITER_LUMO 10000
&OUTER_SCF
EPS_SCF 2.0E-7
MAX_SCF 300
&END OUTER_SCF
! &MIXING
! ALPHA 0.01
! &END
! &DIAGONALIZATION
! ALGORITHM DAVIDSON
! &END
&OT T
MINIMIZER DIIS
PRECONDITIONER FULL_KINETIC ! FULL_ALL
SAFE_DIIS T
&END OT
&END SCF
&XC
&XC_FUNCTIONAL PBE
&END XC_FUNCTIONAL
DENSITY_CUTOFF 1.0000000000000000E-10
GRADIENT_CUTOFF 1.0000000000000000E-10
TAU_CUTOFF 1.0000000000000000E-10
&XC_GRID
XC_SMOOTH_RHO NN50
XC_DERIV NN50_SMOOTH
&END XC_GRID
&END XC
&POISSON
PERIODIC XYZ
&END POISSON
&END DFT
&SUBSYS
&CELL
ABC 1.5200509080292399E+01 3.3000000000000E+01 1.3178605533387005E+01
PERIODIC XYZ
&END CELL
&TOPOLOGY
COORD_FILE_NAME ./mystruc.xyz<http://mystruc.xyz>
COORDINATE XYZ
&END TOPOLOGY
&KIND O
BASIS_SET QZV3P-GTH-q6
POTENTIAL GTH-PBE-q6
&END KIND
&KIND H
BASIS_SET QZV3P-GTH-q1
POTENTIAL GTH-PBE-q1
&END KIND
&END
&END SUBSYS
&PRINT
&TOTAL_NUMBERS ON
&END TOTAL_NUMBERS
&END
&END FORCE_EVAL
Thanks again and best
Daniel
El jueves, 10 de mayo de 2018, 14:23:28 (UTC+2), Matthias Krack escribió:
Dear Daniel
Did you try to restart with DIAGONALISATION and ADDED_MOS using a wavefunction restart file from a well-converged OT run?
Best regards
Matthias
From: cp... at googlegroups.com [mailto:cp... at googlegroups.com] On Behalf Of Dan_M
Sent: 10 May 2018 13:46
To: cp2k
Subject: [CP2K:10298] Re: MO coefficients not normalized?
Thanks a lot Matt for your very fast answer. I was so concerned with technical issues that I forgot about the basics.
Actually maybe you or some other expert can help me out with the actual issue I am having. The situation is this:
I want to get the MOs (eigenvalues and eigenvectors) for both the occupied and unoccupied states in a somewhat involved system (~100-200 waters plus one proton, i.e. total charge +1, geometry let's say far from any local minima). For this I tried two routes:
1) converge the wfn with OT and request NLUMO to be computed after convergence. With this I find two problems:
- The calculation of the LUMOs does not converge (I get "WARNING : did not converge in ot_eigensolver" even if I increase MAX_ITER_LUMO to 1000 which I think should be enough). I note that I could get it converged for EPS_LUMO 1.0E-4 but I tried with a much tighter convergence (2.0E-07 as with the occupied states) since what I get otherwise is the energy of the LUMO below that of the HOMO. I am aware of this happening often when the system is metallic and OT is not well suited but I think it should not happen in a protonated water system (I would expect finding the LUMO as a lone state somewhere in the middle of the band gap, but not this).
- Even when it converges (which I managed to do in toy systems but not on my system of interest), this only works for getting the eigenvalues which can be done either requesting the NLUMO in the &PDOS or in the &MO_CUBES sections, but not the eigenvectors even if I try to do the trick of asking for MO_INDEX_RANGE 1 [nhomo+nlumo] in the &MO section.
2) converge the wfn with diagonalization in any flavor (standard, davidson, lanczos or filter_matrix) requesting ADDED_MOS. Here the problem is that the diagonalization is a complete pain and I am struggling a lot to get it converged, which I did not manage yet. I am trying to do the usual tricks (playing with the ALPHA in &MIXING, etc), but still I have not managed to converge it. I tried doing the trick of computing the wfn with OT and then use that wfn as guess in a run with diagonalization with ADDED_MOS, but in that case the coefficients seem to be rescaled or ignored (since there are less MOS in the restart wfn than expected) and I don't get any improvement.
Maybe somebody could give me some tips for improving the diagonalization in charged systems (some combination of mixing methods, parameters, etc.) or some workaround to make it work with OT?
Thanks again!
D.
El miércoles, 9 de mayo de 2018, 22:21:37 (UTC+2), Matt W escribió:
Dear Daniel,
the Gaussian basis set is not orthonormal, so the overlap matrix is required to provide a metric that converts to an orthonormal basis. Due to symmetry the pz orbital is orthogonal to the others in your example, so in that case every thing is easy.
In general, the relation is C^T S C = I, where C is the matrix of MO coefficients, S is the overlap matrix and I is the identity matrix. You can print of the S matrix and check this. It is somewhere in the AO_MATRICES section of DFT % PRINT.
See, for instance, Szabo and Ostlund, Modern Quantum Chemistry, Introduction to Advanced Electronic Structure Theory - exercise 3.10 in my version.
Matt
On Wednesday, May 9, 2018 at 8:20:13 PM UTC+1, Dan_M wrote:
Dear all,
After requesting the printing out of the MO coefficients, I have observed that the coefficients do not seem to be normalized. For instance, here are the MOs for 1 water molecule with a SZV basis (after a single point calculation on the "real" geometry, with diagonalization algorithm standard):
MO EIGENVALUES, MO OCCUPATION NUMBERS, AND SPHERICAL MO EIGENVECTORS
1 2 3 4
-0.952554 -0.496599 -0.304175 -0.250528
2.000000 2.000000 2.000000 2.000000
1 1 O 2s 0.807460 -0.000000 0.542312 0.000000
2 1 O 3py -0.246487 -0.000000 0.810927 0.000000
3 1 O 3pz -0.000000 0.000000 -0.000000 1.000000
4 1 O 3px 0.000000 -0.661844 -0.000000 -0.000000
5 2 H 1s 0.125677 -0.390214 -0.194623 -0.000000
6 3 H 1s 0.125677 0.390214 -0.194623 -0.000000
So only the MO 4 is trivially normalized, but the others are not. Am I missing something (some correction factor, etc) or is this just the way it is?
Thanks and best
Daniel
--
You received this message because you are subscribed to the Google Groups "cp2k" group.
To unsubscribe from this group and stop receiving emails from it, send an email to cp2k+... at googlegroups.com.
To post to this group, send email to cp... at googlegroups.com.
Visit this group at https://groups.google.com/group/cp2k.
For more options, visit https://groups.google.com/d/optout.
--
You received this message because you are subscribed to the Google Groups "cp2k" group.
To unsubscribe from this group and stop receiving emails from it, send an email to cp2k+... at googlegroups.com<javascript:>.
To post to this group, send email to cp... at googlegroups.com<javascript:>.
Visit this group at https://groups.google.com/group/cp2k.
For more options, visit https://groups.google.com/d/optout.
--
You received this message because you are subscribed to the Google Groups "cp2k" group.
To unsubscribe from this group and stop receiving emails from it, send an email to cp2k+uns... at googlegroups.com<mailto:cp2k+uns... at googlegroups.com>.
To post to this group, send email to cp... at googlegroups.com<mailto:cp... at googlegroups.com>.
Visit this group at https://groups.google.com/group/cp2k.
For more options, visit https://groups.google.com/d/optout.
-------------- next part --------------
An HTML attachment was scrubbed...
URL: <https://lists.cp2k.org/archives/cp2k-user/attachments/20180511/41ed7893/attachment.htm>
More information about the CP2K-user
mailing list