Theory says it is not, at least up to now. Recent experiment showed it is.
I'm not sure to be honest. This is what i actually was looking for:  Where
can i read more about this "switching path"(what is meant by this ?) ? I've
briefly looked up the literature and this is that people do to study
ferroelectrics. Do you know a good review on this subject ?


On Tue, Oct 1, 2013 at 10:01 AM, Pablo Aguado <[email protected]> wrote:

> Is this perovskite ferroelectric? If so you could calculate the
> polarization along the switching path (even if it does not go through a
> high symmetry phase) to get a meaningful value of P.
>
> Pablo
>
>
> On Tue, Oct 1, 2013 at 3:20 PM, Andrei Buin <[email protected]> wrote:
>
>> 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]
>>> ------------------------------------------------------------
>>>
>>
>>
>
>
> --
> -----------------------------------------------------------
> Pablo Aguado Puente
> [email protected]
> ------------------------------------------------------------
>

Responder a