[CP2K:10298] Re: MO coefficients not normalized?
Dan_M
danielm... at gmail.com
Thu May 10 16:04:05 UTC 2018
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
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 <javascript:> [mailto:
> cp... at googlegroups.com <javascript:>] *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 <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.
>
-------------- next part --------------
An HTML attachment was scrubbed...
URL: <https://lists.cp2k.org/archives/cp2k-user/attachments/20180510/1a218a00/attachment.htm>
More information about the CP2K-user
mailing list