Mulliken charge problem

Matthias matthia... at psi.ch
Mon Aug 10 07:11:33 UTC 2009


cp2k/tests/QS/BASIS_MOLOPT

Matthias

On Aug 10, 9:05 am, obo <bo... at matcalc.de> wrote:
> thanks for your answer.
> do you know where i can download a BASIS SET file with these MOLOPT
> basis sets?
>
> Oliver
>
> On 10 Aug., 09:01, Matthias <matthia... at psi.ch> wrote:
>
> > The overlap matrix for such basis sets becomes ill-conditioned. Please
> > note, augmented basis sets as employed for molecular systems are
> > usually not suited for condensed systems and shouldn't be used for
> > such systems. You may try the MOLOPT basis sets e.g. DZVP-MOLOPT-SR-
> > GTH-q4 for Si and DZVP-MOLOPT-SR-GTH-q6 for O for your quartz systems.
>
> > Matthias
>
> > On Aug 10, 8:39 am, obo <bo... at matcalc.de> wrote:
>
> > > I have tested different Basis Sets. With confined Basis Sets the
> > > problem becomes better but there is a difference anymore.
> > > With an augment Basis Set I get the following error:
>
> > >  *** 08:35:30 ERRORL2 in cp_fm_cholesky:cp_fm_cholesky_decompose
> > > err=-300   ***
> > >  *** condition FAILED at line 92
>
> > > I have reada about linear dependences in the BASIS SET. Can somebody
> > > explain me what this means?
> > > thanks
> > > Oliver
>
> > > On 3 Aug., 10:23, obo <bo... at matcalc.de> wrote:
>
> > > > Dear cp2k Users,
> > > > I've made some calculations with alpha quarz. At first I have
> > > > optimized the hexagonal cell with 9 atoms. I've got the initial
> > > > coordinates from a cell optimization in another ab initio programm.
> > > > The relaxation in cp2k was sucessfull and the mulliken charges from
> > > > the Si atoms are approximately the same. Now I have constructed an
> > > > orthorhombic cell with 19 atoms. I've constructed the basis from the
> > > > coordinates of the relaxed hexagonal cell. The length of the cell
> > > > vectors are also calculated from the hexagonal cell vectors(a, 3^0.5,
> > > > c).
> > > > When I start the cell optimization, I get the following mulliken
> > > > charges:
> > > >   Atom     |    Charge
> > > >      1  Si    1.370421
> > > >      2  Si    1.349422
> > > >      3  Si    0.726644
> > > >      4  O    -0.611734
> > > >      5  O    -0.644209
> > > >      6  O    -0.595641
> > > >      7  O    -0.609976
> > > >      8  O    -0.586622
> > > >      9  O    -0.647799
> > > >     10  Si    1.473611
> > > >     11  Si    1.489633
> > > >     12  Si    0.829598
> > > >     13  O    -0.609031
> > > >     14  O    -0.568553
> > > >     15  O    -0.591643
> > > >     16  O    -0.610546
> > > >     17  O    -0.600818
> > > >     18  O    -0.562758
> > > >   Total       0.000000
>
> > > > At the end of the cell optimization, the relation between the cell
> > > > vectors (a and 3^0.5*a) are also wrong.
> > > > What is my mistake??? Can somebody help me?
>
> > > > The input file:
>
> > > > &FORCE_EVAL
> > > >   METHOD Quickstep
> > > >   STRESS_TENSOR NUMERICAL
> > > >   &DFT
> > > >      &POISSON
> > > >        PERIODIC XYZ
> > > >        POISSON_SOLVER PERIODIC
> > > >        &EWALD
> > > >         EWALD_TYPE SPME
> > > >        &END
> > > >      &END POISSON
> > > >     &MGRID
> > > >       CUTOFF 650
> > > >       RELATIVE_CUTOFF 85.0
> > > >     &END MGRID
> > > >     &QS
> > > >      WF_INTERPOLATION PS
> > > >      EXTRAPOLATION_ORDER 4
> > > >     &END QS
> > > >     &SCF
> > > >       EPS_SCF 1.E-6
> > > >       CHOLESKY OFF
> > > >       MAX_SCF 50
> > > >       SCF_GUESS ATOMIC
> > > >       &OUTER_SCF
> > > >         DIIS_BUFFER_LENGTH 5
> > > >         OPTIMIZER DIIS
> > > >       &END OUTER_SCF
> > > >     &END SCF
> > > >     &XC
> > > >        &XC_GRID
> > > >         XC_DERIV SPLINE3
> > > >        &END XC_GRID
> > > >        &XC_FUNCTIONAL PBE
> > > >        &END XC_FUNCTIONAL
> > > >     &END XC
> > > >   &END DFT
> > > >   &SUBSYS
> > > >     &CELL
> > > >       PERIODIC XYZ
> > > >       MULTIPLE_UNIT_CELL 1 1 1
> > > >       ABC 4.805 8.3225 5.393
> > > >       ALPHA_BETA_GAMMA  90.0 90.0 90.0
> > > >     &END CELL
> > > >     &COORD
> > > > Si 1.1328078594000004 6.4061604696       3.5954303785000006
> > > > Si 1.1329589190000002 1.9039591092000003 1.7978168006000006
> > > > Si 2.6289910789000004 8.3163249591       5.3929132817
> > > > O 1.6426232969999999  7.8451213509999995 4.154876766399999
> > > > O 4.4371215705        1.6255884538000005 2.3576057410000004
> > > > O 3.6202186447        7.155568958499999  0.5597043610000001
> > > > O 1.6427913173999997  0.4650789015000002 1.237976828999999
> > > > O 3.620111714099999   1.1547964305000002 4.8334310334
> > > > O 4.4368490245        6.684213627799998  3.035570217399999
> > > > Si 3.4358078594       2.2346604696       3.5954303785000006
> > > > Si 3.435958918999999  6.054959109200001  1.7978168006000006
> > > > Si 0.1269910789       4.144824959099999  5.3929132817
> > > > O 3.9456232970000005  3.6736213510000013 4.154876766399999
> > > > O 1.9351215704999998  5.776588453800002  2.3576057410000004
> > > > O 1.1182186447000002  2.984068958500001  0.5597043610000001
> > > > O 3.9457913174000008  4.616078901500002  1.237976828999999
> > > > O 1.1181117141        5.305796430500002  4.8334310334
> > > > O 1.9348490245        2.5127136278000006 3.035570217399999
> > > >      &END COORD
> > > >     &KIND Si
> > > >       BASIS_SET DZVP-GTH-PBE
> > > >       POTENTIAL GTH-PBE-q4
> > > >     &END KIND
> > > >     &KIND O
> > > >       BASIS_SET DZVP-GTH-PBE
> > > >       POTENTIAL GTH-PBE-q6
> > > >     &END KIND
> > > >     &KIND H
> > > >       BASIS_SET DZVP-GTH-PBE
> > > >       POTENTIAL GTH-PBE-q1
> > > >     &END KIND
> > > >     &TOPOLOGY
> > > >      CENTER_COORDINATES T
> > > >      &DUMP_PDB
> > > >      &END
> > > >        MULTIPLE_UNIT_CELL 1 1 1
> > > >     &END TOPOLOGY
> > > >   &END SUBSYS
> > > > &END FORCE_EVAL
> > > > &GLOBAL
> > > >   PROJECT SiO-Cell
> > > >   RUN_TYPE CELL_OPT
> > > >   PRINT_LEVEL MEDIUM
> > > > &END GLOBAL
> > > > &MOTION
> > > >   &GEO_OPT
> > > >   MAX_ITER 200
> > > >   OPTIMIZER BFGS
> > > >   MAX_FORCE 5.0E-5
> > > >   &END GEO_OPT
> > > >   &CELL_OPT
> > > >    EXTERNAL_PRESSURE [bar] 0.0
> > > >    PRESSURE_TOLERANCE 15.0
> > > >    MAX_ITER 900
> > > >    KEEP_ANGLES TRUE
> > > >    OPTIMIZER CG
> > > >    &CG
> > > >     &LINE_SEARCH
> > > >       TYPE 2PNT
> > > >     &END LINE_SEARCH
> > > >    &END CG
> > > >   &END CELL_OPT
> > > > &END MOTION
>
> > > > thanks
> > > > Oliver
>
>


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