Thank you Pablo. The problem is this particular pervoskite does not have a
centrosymmetric phase. I do realize that polarization is defined modulo x
(since momentum operator defined modulo x), then i have to a have reference
phase(which i dont). Thanks for the corrections for the PolarizationGrid
block. Will try it.

With Best Regards, Andrei Buin.



On Tue, Oct 1, 2013 at 9:13 AM, Pablo Aguado <[email protected]> wrote:

>
> Hi Andrie,
>
> A couple of comments, first the absolute value of the polarization per se
> is only defined modulo a quantum of polarization, so the value you get is P
> = P_"real" + n P_q, where n is an integer number and P_q is the quantum of
> polarization. P_q=e/A where A is the surface area of your unit cell
> perpendicular to the direction with respect to which you are calculating P.
>
> Since you don't know the value of n, to get the value of P_"real" you
> usually calculate the polarization of a reference structure which P is
> known by symmetry (in perovskites for instance, the centrosymetric phase
> has either 0 or P_q/2). Then substracting the P from the centrosymmetric
> you should be able to get the polarization of the polar phase (you might
> still have some problems to identify the "true" polarization if the P of
> the polar phase is comparable or larger than the quantum, see this
> introductory paper for more details http://arxiv.org/abs/1202.1831)
>
> Another issue is the PolarizationGrid block you are using, which is the
> example in the siesta manual and might not be the most suitable for you
> simulation cell. Something like this would make more sense (re-read the
> manual entry for the meaning of this block):
>
>  %block PolarizationGrids
>         20   4  4      yes
>          4  20  4      yes
>          4   4 15      yes
> %endblock PolarizationGrids
>
> Best regards,
>
> Pablo
>
>
> On Tue, Oct 1, 2013 at 2:39 PM, Andrei Buin <[email protected]> wrote:
>
>> Dear Siesta forum,
>>
>> I have 48(pervoskite CH3NH3PbI3) atoms in the 9 Angs x 9 Angs x 12 Angs
>> unit cell.
>> I'm trying to compute the Berry phase polarization usign
>> PolarizationGrids, and i get
>> insane dipole moment of:
>>
>> siesta: Macroscopic polarization per unit cell (Debye):
>> siesta: Along the lattice vectors   2742.652644 2679.284584 4191.471845
>> siesta: Along cartesian directions  2742.652644 2679.284584 4191.471845
>>
>>
>>
>> Input is attached. Forces are already converged.
>>
>> # 6.2 General System descriptors
>>
>> SystemName          Tetra Super Unit Cell Siesta Calculations
>> SystemLabel          Tet   # Short name for naming files
>> NumberOfSpecies      5
>> NumberOfAtoms        48
>>
>> %block Chemical_Species_Label
>>   1   82   Pb
>>   2   53   I
>>   3   7    N
>>   4   6    C
>>   5   1    H
>> %endblock Chemical_Species_Label
>>
>>
>>
>>
>> # 6.3 Basis definitions
>>
>> PAO.BasisSize        DZP
>> PAO.EnergyShift      65 meV
>> #PAO.SplitNorm        0.15
>> PAO.SplitTailNorm true
>> PAO.SoftDefault true
>> PAO.OldStylePolOrbs false
>>
>> %block PS.KBprojectors
>>   I    4
>>    0     2
>>    2000 -2000
>>    1     2
>>    2000 -2000
>>    2     2
>>    2000 -2000
>>   3     1
>>    2000
>>
>>
>>   Pb    4
>>    0     2
>>    2000  -2000
>>    1     2
>>    2000  -2000
>>    2     2
>>    2000  -2000
>>    3     1
>>    2000
>>
>>   N    4
>>    0     2
>>    2000  -2000
>>    1     2
>>    2000  -2000
>>    2     2
>>    2000  -2000
>>    3     1
>>    2000
>>
>>   H    3
>>    0     2
>>    2000 -2000
>>    1     2
>>    2000 -2000
>>    2     1
>>    2000
>>
>>   C    4
>>    0     2
>>    2000 -2000
>>    1     2
>>    2000 -2000
>>    2     2
>>    2000 -2000
>>    3     1
>>    2000
>> %endblock PS.KBprojectors
>>
>>
>>
>> %block PAO.Basis                 # Define Basis set
>> Pb          3                    # Species label, number of l-shells
>>  n=6   0   2                    # n, l, Nzeta, Polarization, NzetaPol
>>    0      0
>>  n=6   1   2      P  1                   # n, l, Nzeta, Polarization,
>> NzetaPol
>>    0      0
>>  n=5   2   1  # SZ for 5d
>>    0      #0
>>
>>
>> # H in C6H6 DZP
>> #Vova
>> H    2      0.00000
>>  n=1   0   2   E    11.36136     0.00928
>>      7.72405     2.19949
>>  n=2   1   1   E    41.15301     0.00947
>>      2.89938
>>
>>
>> # C in C6H6 DZP
>> #Vova
>> C    3      0.00000
>>  n=2   0   2   E    39.65304     6.21693
>>      7.40483     4.90026
>>  n=2   1   2   E    27.05294     3.74121
>>      7.88345     3.11808
>>  n=3   2   1   E    55.60264     0.01540
>>      3.93573
>> %endblock PAO.Basis
>>
>>
>>
>>
>>
>> # 6.4 Lattice, coordinates, k-sampling
>>
>> LatticeConstant     8.96 Ang   # 6.05 350Ry, 5.93845 Ang Exp, 5.936 Exp,
>> 5.84_LDA_Zhenya
>>
>> %block LatticeVectors
>>    1.0 0 0 #18A crystal + 12Avacuum
>>    0 1.0 0
>>    0 0 1.4375
>> %endblock LatticeVectors
>>
>> AtomicCoordinatesFormat    Ang
>> AtomicCoorFormatOut        Ang
>>
>>
>>
>>
>>
>>
>>
>>
>>
>> %block AtomicCoordinatesAndAtomicSpecies
>>     -0.03167    -0.11487    -0.35971 1
>>     -0.12412    -0.42211     2.92565 2
>>      1.85899     2.43724    -0.06194 2
>>      4.40361     4.31212    -0.38969 1
>>      6.99200     6.23198    -0.88879 2
>>      2.46456     6.94775    -0.15215 2
>>      6.36927     1.84289     0.08180 2
>>     -0.09247    -0.14207     6.12437 1
>>      2.57611     1.64461     5.69084 2
>>      4.35503     4.31005     6.09334 1
>>      6.18152     6.97008     6.46046 2
>>      4.59235     4.49865     2.91059 2
>>      4.43687     3.75124     9.32494 2
>>      0.44143    -0.12135     9.34642 2
>>      3.78065     0.42371     2.39084 3
>>      4.82458    -0.31863     3.15069 4
>>      3.28270    -0.20569     1.72441 5
>>      4.20292     1.18515     1.82761 5
>>      3.08493     0.84035     3.03696 5
>>      5.25142     0.34763     3.90531 5
>>      5.60253    -0.63714     2.45202 5
>>      4.36520    -1.18663     3.63088 5
>>      4.08008     0.15264     8.72657 3
>>      4.82907    -0.48545     9.84708 4
>>      4.39959    -0.21875     7.81266 5
>>      4.21776     1.18640     8.72722 5
>>      3.05391    -0.01415     8.80689 5
>>      4.48385    -0.06168    10.79380 5
>>      5.89626    -0.28577     9.71242 5
>>      4.64461    -1.56270     9.82703 5
>>     -0.85527     5.05646     2.32772 3
>>      0.08950     4.13502     3.02005 4
>>     -0.81071     4.97580     1.29648 5
>>     -0.65212     6.05774     2.55366 5
>>     -1.84958     4.87012     2.59300 5
>>     -0.01489     4.27318     4.09978 5
>>      1.10925     4.37398     2.70535 5
>>     -0.15654     3.10553     2.74484 5
>>      7.04591     2.46318     6.25281 2
>>      1.72806     6.16802     6.24656 2
>>     -0.59017     4.78536     8.67712 3
>>      0.30844     3.96725     9.53987 4
>>     -1.16287     4.17787     8.05170 5
>>     -0.03405     5.40998     8.05433 5
>>     -1.22474     5.36318     9.25668 5
>>      0.88403     4.63525    10.18598 5
>>      0.97946     3.39039     8.89784 5
>>     -0.30006     3.29480    10.15037 5
>> %endblock AtomicCoordinatesAndAtomicSpecies
>>
>>
>> #%block GeometryConstraints
>> #position 1 2
>> #%endblock GeometryConstraints
>>
>> #kgrid_cutoff    20 Ang
>>
>> #BandLinesScale  pi/a
>> #BandLinesScale ReciprocalLatticeVectors
>>
>> #%block BandLines
>> #1 1 1 1 L
>> #20 0 0 0 G
>> #20 1.5 0 1.5 K
>> #10 2 0 0 X
>> #20 0 0 0 G
>> #%endblock Bandlines
>>
>> %block kgrid_Monkhorst_Pack
>>  8 0 0 0
>>  0 8 0 0
>>  0 0 8 0
>> %endblock kgrid_Monkhorst_Pack
>>
>>
>>
>>
>> # 6.5 DFT, Grid, SCF
>>
>> XC.functional       GGA
>> XC.authors          PBE
>> #SpinPolarized       true
>> MeshCutoff          375 Ry
>> FilterCutoff        375 Ry
>> MaxSCFIterations    199         # Maximum number of SCF iter
>> DM.MixingWeight     0.05         # New DM amount for next SCF cycle
>> DM.NumberPulay      10
>> DM.PulayOnFile      false
>> DM.NumberKick       50
>> #DM.KickMixingWeight 0.1
>> #DM.Tolerance    0.00001  # 0.0004
>> #DM.EnergyTolerance 0.00005 eV
>>
>>
>>
>>
>>
>> #%block PolarizationGrids
>> #   7 3 3 yes
>> #   3 7 3 yes
>> #   3 3 7 yes
>> #%endblock PolarizationGrids
>>
>>
>>  %block PolarizationGrids
>>         10   3  4      yes
>>          2  20  2       no
>>          4   4 15
>> %endblock PolarizationGrids
>>
>>
>>
>> # 6.6 Eigenvalue problem: order-N or diagonalization
>>
>> SolutionMethod         diagon
>> #Diag.DivideAndConquer  false
>> #NumberOfEigenStates    10000   # total is ~27000 SZ
>> #OccupationFunction     MP
>> #OccupationMPOrder      1
>> #ElectronicTemperature  300 K
>> #ON.ChemicalPotentialUse   true
>>
>>
>>
>> # 6.7 Molecular dynamics and relaxations
>>
>> MD.TypeOfRun           CG
>> #MD.NoseMass            600 Ry*fs**2
>>
>> MD.NumCGsteps         9950
>> MD.MaxCGDispl         0.15  Ang
>> MD.MaxForceTol        0.040 eV/Ang
>>
>> #MD.LengthTimeStep      1 fs
>> #MD.FinalTimeStep       10000
>> #MD.InitialTemperature  550 K
>> #MD.TargetTemperature   550 K
>>
>>
>>
>>
>>
>>
>> # 6.8 Parallel options
>>
>> #BlockSize       426 # for 16 procs #852 for 8 # DZP 6813 orbitals
>> #ProcessorY      8
>> #Diag.Memory     4
>> #Diag.ParallelOverK    true
>>
>>
>>
>> # 6.9 Efficiency options
>>
>> # 6.10 Output options
>>
>> WriteMDXmol     true
>> WriteCoorXmol   true
>> WriteMDhistory  true
>> WriteXML        false
>> #WriteForces     true
>> #WriteMullikenPop   1
>>
>>
>>
>>
>> # 6.11 Options for saving/reading information
>> UseSaveData      true
>> MD.UseSaveCG     true
>>
>> #SaveRho          true
>> #SaveDeltaRho     true
>> #SaveElectrostaticPotential     true
>> #SaveTotalPotential true
>> #SaveIonicCharge   true
>> #SaveTotalCharge   true
>>
>> %block LocalDensityOfStates
>>   -7.15    12.00   eV
>> %endblock LocalDensityOfStates
>>
>> %block ProjectedDensityOfStates
>>   -7.0   12.0   0.05   521  eV #min, max, broaden 100meV, steps every
>> 25meV
>> %endblock ProjectedDensityOfStates
>>
>>
>> #WriteDenchar         true
>>
>> #%block WaveFuncKPoints
>> # 0.0 0.0 0.0    from 1040 to 1055 # traps # HOMO 1042
>> #%endblock WaveFuncKpoints
>>
>>
>> #OpticalCalculation      true
>> #Optical.EnergyMinimum   0 eV
>> #ptical.EnergyMaximum   4.5 eV
>> #Optical.Broaden         0.01 eV
>> #Optical.NumberOfBands   1100   # LUMO 1085
>>
>>
>
>
> --
> -----------------------------------------------------------
> Pablo Aguado Puente
> [email protected]
> ------------------------------------------------------------
>

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