[gpaw-users] Strange feature from time propagation TDDFT

Arto Sakko arto.sakko at aalto.fi
Wed Jul 4 13:49:47 CEST 2012


Dear gpaw-users,

  I am calculating the photoabsorption spectrum using the time 
propagation TDDFT method. I find a strange feature in the 60-70 eV 
regime when the system contains gold or silver atoms. The continuum part 
of the spectrum always contains unphysical peaks (standing waves), but 
this seems different. For example, the f-sum rule is not obeyed because 
of this peak (the value of the integrated spectrum is too large by 
several electrons). The low-energy part of the spectrum is ok, but I 
would like to understand the origin of this peak, partly because I am 
also interested in the features at the high energy range.

  I attach an example script (silver dimer) for generating that peak, as 
well as standard output and a figure of the resulting spectrum.

  The feature appears also with smaller time steps, smaller spacings, 
and larger box sizes. Is there an explanation for this feature?

With best regards,
  Arto Sakko

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 |___|_|             

User:  sakkoa1 at cn127
Date:  Wed Jul  4 10:05:18 2012
Arch:  x86_64
Pid:   17559
Dir:   /triton/tfy/work/sakkoa1/Programs/gpaw/gpaw-web/build/lib.linux-x86_64-2.6/gpaw
ase:   /cvmfs/fgi.csc.fi/apps/ase/3.6.0/ase (version 3.6.0.2515)
numpy: /usr/lib64/python2.6/site-packages/numpy (version 1.3.0)
units: Angstrom and eV
cores: 12

Memory estimate
---------------
Process memory now: 35.72 MiB
Calculator  1.80 MiB
    Density  0.76 MiB
        Arrays  0.27 MiB
        Localized functions  0.44 MiB
        Mixer  0.06 MiB
    Hamiltonian  0.42 MiB
        Arrays  0.18 MiB
        XC  0.00 MiB
        Poisson  0.21 MiB
        vbar  0.03 MiB
    Wavefunctions  0.62 MiB
        Arrays psit_nG  0.17 MiB
        Eigensolver  0.21 MiB
        Projectors  0.08 MiB
        Overlap op  0.17 MiB

Positions:
  0 Ag    2.7350    3.0000    3.0000
  1 Ag    5.2650    3.0000    3.0000

     .-------------------.  
    /|                   |  
   / |                   |  
  /  |                   |  
 *   |                   |  
 |   |                   |  
 |   |    Ag    Ag       |  
 |   .-------------------.  
 |  /                   /   
 | /                   /    
 |/                   /     
 *-------------------*      

Unit Cell:
           Periodic     X           Y           Z      Points  Spacing
  --------------------------------------------------------------------
  1. axis:    no     8.000000    0.000000    0.000000    32     0.2500
  2. axis:    no     0.000000    6.000000    0.000000    24     0.2500
  3. axis:    no     0.000000    0.000000    6.000000    24     0.2500

Ag-setup:
  name   : Silver
  id     : aac732a7f42225a52edcbbb6e277d3cd
  Z      : 47
  valence: 11
  core   : 36
  charge : 0.0
  file   : /cvmfs/fgi.csc.fi/apps/gpaw/gpaw-setups-0.8.7929/Ag.LDA.gz
  cutoffs: 1.30(comp), 2.31(filt), 2.78(core), lmax=2
  valence states:
            energy   radius
    5s(1)   -4.708   1.296
    5p(0)   -0.844   1.296
    4d(10)  -7.664   1.296
    *s      22.503   1.296
    *p      26.368   1.296
    *d      19.547   1.296

Using partial waves for Ag as LCAO basis

Using the LDA Exchange-Correlation Functional.
Spin-Paired Calculation
Total Charge:      0.000000
Fermi Temperature: 0.000000
Wave functions: Uniform real-space grid
Kinetic energy operator: 6*3+1=19 point O(h^6) finite-difference Laplacian
Eigensolver:       rmm-diis
XC and Coulomb potentials evaluated on a 64*48*48 grid
Interpolation: tri-quintic (5. degree polynomial)
Poisson solver: Jacobi solver with 5 multi-grid levels
Stencil: 6*3+1=19 point O(h^6) finite-difference Laplacian
Reference Energy:  -288929.166771

Total number of cores used: 12
Domain Decomposition: 3 x 2 x 2
MatrixOperator buffer_size: default value or 
                            see value of nblock in input file
Diagonalizer layout: Serial LAPACK
Orthonormalizer layout: Serial LAPACK

Symmetries present: 1
1 k-point (Gamma)
1 k-point in the Irreducible Part of the Brillouin Zone
Linear Mixing Parameter:           0.25
Pulay Mixing with 3 Old Densities
No Damping of Long Wave Oscillations

Convergence Criteria:
Total Energy Change:           0.0005 eV / electron
Integral of Absolute Density Change:    0.0001 electrons
Integral of Absolute Eigenstate Change: 4e-08 eV^2
Number of Atoms: 2
Number of Atomic Orbitals: 18
Number of Bands in Calculation:         18
Bands to Converge:                      Occupied States Only
Number of Valence Electrons:            22
                     log10-error:    Total        Iterations:
           Time      WFS    Density  Energy       Fermi  Poisson
iter:   1  10:05:19  +2.3              -1.509548  0      12     
iter:   2  10:05:19  +0.0              -2.447504  0             
iter:   3  10:05:19  -1.1              -2.527664  0             
iter:   4  10:05:20  -1.3   -1.3       -2.277267  0      7      
iter:   5  10:05:20  -1.0   -1.5       -2.191553  0      7      
iter:   6  10:05:20  -1.7   -2.2       -2.229288  0      6      
iter:   7  10:05:20  -2.0   -2.4       -2.238248  0      5      
iter:   8  10:05:20  -2.6   -2.7       -2.238699  0      5      
iter:   9  10:05:20  -2.6   -2.8       -2.239669  0      4      
iter:  10  10:05:20  -3.8   -3.0       -2.239738  0      4      
iter:  11  10:05:20  -4.0   -3.1       -2.239135  0      5      
iter:  12  10:05:20  -4.8   -3.7       -2.239199  0      3      
iter:  13  10:05:20  -5.1   -4.1       -2.239254  0      3      
iter:  14  10:05:21  -5.6   -4.3       -2.239035  0      1      
iter:  15  10:05:21  -6.0   -4.4       -2.239207  0      2      
iter:  16  10:05:21  -6.6   -4.7       -2.239383  0      1      
iter:  17  10:05:21  -6.4   -4.8       -2.239606  0      1      
iter:  18  10:05:21  -7.3   -5.2       -2.239253  0      1      
iter:  19  10:05:21  -6.7   -5.1       -2.239385  0      1      
iter:  20  10:05:21  -8.2   -5.0       -2.239195  0      1      
------------------------------------
Converged After 20 Iterations.

Energy Contributions Relative to Reference Atoms:(reference = -288929.166771)
-------------------------
Kinetic:         +1.092416
Potential:       -1.051590
External:        +0.000000
XC:              -2.384707
Entropy (-ST):   -0.000000
Local:           +0.104686
-------------------------
Free Energy:     -2.239195
Zero Kelvin:     -2.239195

Fermi Level: -3.82729
 Band   Eigenvalues  Occupancy
   0     -8.24284     2.00000
   1     -7.69906     2.00000
   2     -7.69906     2.00000
   3     -7.13898     2.00000
   4     -7.13757     2.00000
   5     -6.92557     2.00000
   6     -6.92349     2.00000
   7     -6.63739     2.00000
   8     -6.63739     2.00000
   9     -6.47296     2.00000
  10     -5.00584     2.00000
  11     -2.64873     0.00000
  12      0.05614     0.00000
  13      0.05614     0.00000
  14      0.74302     0.00000
  15      2.36074     0.00000
  16      2.36074     0.00000
  17      7.23839     0.00000


Total Charge:  -0.000000 electrons
Dipole Moment: [  1.53926251e-13   1.00698319e-13   1.00874570e-13]

  ___ ___ ___ _ _ _  
 |   |   |_  | | | | 
 | | | | | . | | | | 
 |__ |  _|___|_____|  0.10.0.9137
 |___|_|             

User:  sakkoa1 at cn127
Date:  Wed Jul  4 10:05:21 2012
Arch:  x86_64
Pid:   17559
Dir:   /triton/tfy/work/sakkoa1/Programs/gpaw/gpaw-web/build/lib.linux-x86_64-2.6/gpaw
ase:   /cvmfs/fgi.csc.fi/apps/ase/3.6.0/ase (version 3.6.0.2515)
numpy: /usr/lib64/python2.6/site-packages/numpy (version 1.3.0)
units: Angstrom and eV
cores: 12

Memory estimate
---------------
Process memory now: 45.01 MiB
Calculator  2.30 MiB
    Density  0.71 MiB
        Arrays  0.27 MiB
        Localized functions  0.44 MiB
        Mixer  0.00 MiB
    Hamiltonian  0.42 MiB
        Arrays  0.18 MiB
        XC  0.00 MiB
        Poisson  0.21 MiB
        vbar  0.03 MiB
    Wavefunctions  1.17 MiB
        Arrays psit_nG  0.33 MiB
        Eigensolver  0.42 MiB
        Projectors  0.08 MiB
        Overlap op  0.34 MiB
     .-------------------.  
    /|                   |  
   / |                   |  
  /  |                   |  
 *   |                   |  
 |   |                   |  
 |   |    Ag    Ag       |  
 |   .-------------------.  
 |  /                   /   
 | /                   /    
 |/                   /     
 *-------------------*      

Unit Cell:
           Periodic     X           Y           Z      Points  Spacing
  --------------------------------------------------------------------
  1. axis:    no     8.000000    0.000000    0.000000    32     0.2500
  2. axis:    no     0.000000    6.000000    0.000000    24     0.2500
  3. axis:    no     0.000000    0.000000    6.000000    24     0.2500

Ag-setup:
  name   : Silver
  id     : aac732a7f42225a52edcbbb6e277d3cd
  Z      : 47
  valence: 11
  core   : 36
  charge : 0.0
  file   : /cvmfs/fgi.csc.fi/apps/gpaw/gpaw-setups-0.8.7929/Ag.LDA.gz
  cutoffs: 1.30(comp), 2.31(filt), 2.78(core), lmax=2
  valence states:
            energy   radius
    5s(1)   -4.708   1.296
    5p(0)   -0.844   1.296
    4d(10)  -7.664   1.296
    *s      22.503   1.296
    *p      26.368   1.296
    *d      19.547   1.296

Using partial waves for Ag as LCAO basis

Using the LDA Exchange-Correlation Functional.
Spin-Paired Calculation
Total Charge:      0.000000
Fermi Temperature: 0.000000
Wave functions: Uniform real-space grid
Kinetic energy operator: 6*3+1=19 point O(h^6) finite-difference Laplacian
Eigensolver:       rmm-diis
XC and Coulomb potentials evaluated on a 64*48*48 grid
Interpolation: tri-quintic (5. degree polynomial)
Poisson solver: Jacobi solver with 5 multi-grid levels
Stencil: 6*3+1=19 point O(h^6) finite-difference Laplacian
Reference Energy:  -288929.166771

Total number of cores used: 12
Domain Decomposition: 3 x 2 x 2
MatrixOperator buffer_size: default value or 
                            see value of nblock in input file
Diagonalizer layout: Serial LAPACK
Orthonormalizer layout: Serial LAPACK

Symmetries present: 1
1 k-point (Gamma)
1 k-point in the Irreducible Part of the Brillouin Zone
Linear Mixing Parameter:           0.1
Pulay Mixing with 3 Old Densities
Damping of Long Wave Oscillations: 50

Convergence Criteria:
Total Energy Change:           0.0005 eV / electron
Integral of Absolute Density Change:    0.0001 electrons
Integral of Absolute Eigenstate Change: 4e-08 eV^2
Number of Atoms: 2
Number of Atomic Orbitals: 18
Number of Bands in Calculation:         18
Bands to Converge:                      Occupied States Only
Number of Valence Electrons:            22

Positions:
  0 Ag    2.7350    3.0000    3.0000
  1 Ag    5.2650    3.0000    3.0000



------------------------------------------
  Time-propagation TDDFT                  
------------------------------------------

Charge epsilon:  1e-05
Solver:  CSCG
Preconditioner:  None
Propagator:  SICN
States per processor =  18
Delta kick =  (0.001, 0.0, 0.0)

Starting time:    0.00 as
Time step:       10.00 as

                        Simulation      Total        log10     Iterations:
             Time          time         Energy       Norm      Propagator
iter:   0  10:05:23        0.00       -0.082278     -13.3          0
iter:  10  10:05:31      100.00       -0.082278     -13.4         73
iter:  20  10:05:40      200.00       -0.082278     -13.5         73
iter:  30  10:05:48      300.00       -0.082278     -13.5         72
iter:  40  10:05:56      400.00       -0.082278     -13.3         71
iter:  50  10:06:05      500.00       -0.082278     -13.2         73
iter:  60  10:06:13      600.00       -0.082278     -13.6         70
iter:  70  10:06:21      700.00       -0.082278     -13.2         71
iter:  80  10:06:30      800.00       -0.082278     -13.3         70
iter:  90  10:06:38      900.00       -0.082278     -13.5         72
iter: 100  10:06:46     1000.00       -0.082278     -13.2         73
iter: 110  10:06:55     1100.00       -0.082278     -13.4         72
iter: 120  10:07:03     1200.00       -0.082278     -13.3         70
iter: 130  10:07:11     1300.00       -0.082278     -13.5         71
iter: 140  10:07:20     1400.00       -0.082278     -13.5         74
iter: 150  10:07:28     1500.00       -0.082278     -13.4         71
iter: 160  10:07:37     1600.00       -0.082278     -13.5         73
iter: 170  10:07:45     1700.00       -0.082278     -13.4         72
iter: 180  10:07:54     1800.00       -0.082278     -13.6         69
iter: 190  10:08:02     1900.00       -0.082278     -13.3         70
iter: 200  10:08:11     2000.00       -0.082278     -13.3         72
iter: 210  10:08:19     2100.00       -0.082278     -13.3         70
iter: 220  10:08:27     2200.00       -0.082278     -13.4         73
iter: 230  10:08:36     2300.00       -0.082278     -13.4         73
iter: 240  10:08:44     2400.00       -0.082278     -13.4         72
iter: 250  10:08:53     2500.00       -0.082278     -13.7         72
iter: 260  10:09:01     2600.00       -0.082278     -13.3         72
iter: 270  10:09:09     2700.00       -0.082278     -13.8         70
iter: 280  10:09:18     2800.00       -0.082278     -13.5         70
iter: 290  10:09:26     2900.00       -0.082278     -13.2         74
Calculating photoabsorption spectrum from file "dm.dat"
Using kick strength =  [ 0.001  0.     0.   ]
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 
Calculated photoabsorption spectrum saved to file "spec.txt"
Memory usage: 46.41 MB

============================================================
Timing:                                 incl.     excl.
============================================================
Apply approximate inverse overlap:      0.032     0.032   0.0% |
Apply time-dependent operators:         0.082     0.065   0.0% |
 Apply overlap:                         0.017     0.017   0.0% |
CSCG:                                   0.933     0.215   0.1% |
 Apply time-dependent operators:        0.703     0.559   0.2% |
  Apply overlap:                        0.144     0.144   0.1% |
 Solve TDDFT preconditioner:            0.015     0.015   0.0% |
Hamiltonian:                            0.105     0.000   0.0% |
 Atomic:                                0.000     0.000   0.0% |
 Communicate energies:                  0.059     0.059   0.0% |
 Hartree integrate/restrict:            0.001     0.001   0.0% |
 Initialize Hamiltonian:                0.002     0.002   0.0% |
 Poisson:                               0.040     0.040   0.0% |
 XC 3D grid:                            0.003     0.003   0.0% |
 vbar:                                  0.000     0.000   0.0% |
Propagate:                            251.839     2.490   1.0% |
 Apply approximate inverse overlap:     1.976     1.976   0.8% |
 Apply time-dependent operators:        4.008     2.928   1.2% |
  Apply overlap:                        1.080     1.080   0.4% |
 CSCG:                                193.786    56.038  22.1% |--------|
  Apply time-dependent operators:     133.216    95.453  37.6% |--------------|
   Apply overlap:                      37.763    37.763  14.9% |-----|
  Solve TDDFT preconditioner:           4.532     4.532   1.8% ||
 Density:                               0.056     0.001   0.0% |
  Atomic density matrices:              0.000     0.000   0.0% |
  Mix:                                  0.024     0.024   0.0% |
  Multipole moments:                    0.020     0.020   0.0% |
  Pseudo density:                       0.011     0.011   0.0% |
   Symmetrize density:                  0.000     0.000   0.0% |
 Hamiltonian:                           2.139     0.006   0.0% |
  Atomic:                               0.000     0.000   0.0% |
  Communicate energies:                 1.789     1.789   0.7% |
  Hartree integrate/restrict:           0.015     0.015   0.0% |
  Poisson:                              0.247     0.247   0.1% |
  XC 3D grid:                           0.079     0.079   0.0% |
  vbar:                                 0.004     0.004   0.0% |
 Update time-dependent operators:      47.383     0.875   0.3% |
  Density:                              1.132     0.012   0.0% |
   Atomic density matrices:             0.006     0.006   0.0% |
   Mix:                                 0.492     0.492   0.2% |
   Multipole moments:                   0.402     0.402   0.2% |
   Pseudo density:                      0.220     0.212   0.1% |
    Symmetrize density:                 0.008     0.008   0.0% |
  Hamiltonian:                         45.376     0.126   0.0% |
   Atomic:                              0.003     0.003   0.0% |
   Communicate energies:               35.898    35.898  14.2% |-----|
   Hartree integrate/restrict:          0.295     0.295   0.1% |
   Poisson:                             7.393     7.393   2.9% ||
   XC 3D grid:                          1.583     1.583   0.6% |
   vbar:                                0.079     0.079   0.0% |
Read:                                   0.004     0.001   0.0% |
 Atomic matrices:                       0.001     0.001   0.0% |
 Band energies:                         0.000     0.000   0.0% |
 Projections:                           0.000     0.000   0.0% |
 Pseudo-density:                        0.002     0.002   0.0% |
 Pseudo-potential:                      0.001     0.001   0.0% |
 Pseudo-wavefunctions:                  0.000     0.000   0.0% |
Redistribute:                           0.000     0.000   0.0% |
Symmetrize density:                     0.000     0.000   0.0% |
Update time-dependent operators:        0.016     0.016   0.0% |
Other:                                  0.601     0.601   0.2% |
============================================================
Total:                                          253.614 100.0%
============================================================
date: Wed Jul  4 10:09:35 2012
Memory usage: 46.41 MB

============================================================
Timing:                               incl.     excl.
============================================================
IO:                                   0.151     0.000   0.0% |
 Write:                               0.151     0.000   0.0% |
  Atomic matrices:                    0.000     0.000   0.0% |
  Band energies:                      0.000     0.000   0.0% |
  Close:                              0.001     0.001   0.0% |
  Meta data:                          0.133     0.133   0.1% |
  Projections:                        0.000     0.000   0.0% |
  Pseudo-density:                     0.001     0.001   0.0% |
  Pseudo-potential:                   0.001     0.001   0.0% |
  Pseudo-wavefunctions:               0.014     0.014   0.0% |
Initialization:                       1.437     1.240   0.5% |
 Hamiltonian:                         0.104     0.000   0.0% |
  Atomic:                             0.000     0.000   0.0% |
  Communicate energies:               0.058     0.058   0.0% |
  Hartree integrate/restrict:         0.000     0.000   0.0% |
  Initialize Hamiltonian:             0.002     0.002   0.0% |
  Poisson:                            0.040     0.040   0.0% |
  XC 3D grid:                         0.003     0.003   0.0% |
  vbar:                               0.000     0.000   0.0% |
 LCAO initialization:                 0.093     0.082   0.0% |
  LCAO eigensolver:                   0.002     0.000   0.0% |
   Atomic Hamiltonian:                0.000     0.000   0.0% |
   Calculate projections:             0.000     0.000   0.0% |
   Distribute overlap matrix:         0.001     0.001   0.0% |
   Orbital Layouts:                   0.000     0.000   0.0% |
   Potential matrix:                  0.000     0.000   0.0% |
  LCAO to grid:                       0.001     0.001   0.0% |
  Set positions (LCAO WFS):           0.008     0.007   0.0% |
   Basic WFS set positions:           0.000     0.000   0.0% |
   Basis functions set positions:     0.000     0.000   0.0% |
   TCI: Calculate S, T, P:            0.001     0.001   0.0% |
SCF-cycle:                            1.625     0.011   0.0% |
 Density:                             0.032     0.000   0.0% |
  Atomic density matrices:            0.000     0.000   0.0% |
  Mix:                                0.020     0.020   0.0% |
  Multipole moments:                  0.008     0.008   0.0% |
  Pseudo density:                     0.003     0.002   0.0% |
   Symmetrize density:                0.000     0.000   0.0% |
 Hamiltonian:                         1.262     0.004   0.0% |
  Atomic:                             0.000     0.000   0.0% |
  Communicate energies:               1.011     1.011   0.4% |
  Hartree integrate/restrict:         0.008     0.008   0.0% |
  Poisson:                            0.193     0.193   0.1% |
  XC 3D grid:                         0.044     0.044   0.0% |
  vbar:                               0.002     0.002   0.0% |
 Orthonormalize:                      0.035     0.001   0.0% |
  Band Layouts:                       0.001     0.000   0.0% |
   Inverse Cholesky:                  0.001     0.001   0.0% |
  calc_s_matrix:                      0.021     0.021   0.0% |
  projections:                        0.007     0.007   0.0% |
  rotate_psi:                         0.005     0.005   0.0% |
 RMM-DIIS:                            0.244     0.092   0.0% |
  Apply hamiltonian:                  0.024     0.024   0.0% |
  precondition:                       0.121     0.121   0.0% |
  projections:                        0.007     0.007   0.0% |
 Subspace diag:                       0.042     0.001   0.0% |
  Band Layouts:                       0.003     0.000   0.0% |
   Diagonalize:                       0.002     0.002   0.0% |
   Distribute results:                0.000     0.000   0.0% |
  calc_h_matrix:                      0.030     0.007   0.0% |
   Apply hamiltonian:                 0.023     0.023   0.0% |
  rotate_psi:                         0.009     0.009   0.0% |
Other:                              253.713   253.713  98.7% |--------------------------------------|
============================================================
Total:                                        256.925 100.0%
============================================================
date: Wed Jul  4 10:09:35 2012
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