[CPMD-list] convergence problem on iron porphyrin

Yong Zhang zhangymall11 at gmail.com
Fri Jul 28 20:05:18 CEST 2006


Hello CPMDers,

I am trying to run some simulation on a Fe-porphyrin complex. The
wavefunction optimation did not tend to converge at all. I took an optimized
structure from MM calculation as the initial input. The triplet was reported
before as the stable state of this complex and singlet and quintet are also
possible. I tried all the three states but the results are similar.

The input file is like below.
=============
&INFO
 isolated porphyrin
&END

&CPMD
  OPTIMIZE WAVEFUNCTION
  CONVERGENCE
  1.0e-5 1.0e-4
  LSD
&END

&SYSTEM
  ANGSTROM
  MULTIPLICITY
  3
  SYMMETRY
  0
  CELL
  20.0  1.0  1.0  0  0  0
  CUTOFF
  120.0
&END

&DFT
  NEWCODE
  FUNCTIONAL BLYP
  GC-CUTOFF
  5.0e-6
&END

&ATOMS

*H_MT_BLYP.psp   KLEINMAN-BYLANDER
   LMAX=S
   12
   3.31669  -2.94334   -.16809
   2.93762   3.31304   -.05977
  -3.31384   2.94309    .22042
  -2.92849  -3.31383    .22766
   4.90231   1.61056    .04513
   5.06326  -1.01897   -.00553
   1.02859   5.04983    .27002
  -1.59946   4.89625    .38278
  -5.03348   1.01638    .55312
  -4.86935  -1.61344    .56109
   -.99586  -5.05269    .33204
   1.62901  -4.89882    .16066

*C_MT_BLYP.psp   KLEINMAN-BYLANDER
   LMAX=P
   20
   2.81762   -.90741   -.30078
   4.15831   -.42048   -.10975
   4.07679    .91069   -.08405
   2.68646   1.23777   -.26039
    .89704   2.82649   -.15632
    .42262   4.15497    .12858
   -.90781   4.07726    .18562
  -1.24684   2.70101   -.06341
  -2.83315    .90877    .01509
  -4.14547    .41936    .34573
  -4.06234   -.91195    .34981
  -2.69949  -1.23663    .02068
   -.91015  -2.82534   -.08494
   -.40832  -4.15621    .13424
    .92048  -4.07836    .04743
   1.23122  -2.69964   -.22383
   2.50103  -2.22388   -.22696
   2.21409   2.50419   -.15282
  -2.50975   2.22465    .06664
  -2.21889  -2.50376    .06438

*N_MT_BLYP.psp   KLEINMAN-BYLANDER
   LMAX=P
   4
   1.89556    .11563   -.42853
   -.13402   1.91752   -.31014
  -1.93090   -.11253   -.22157
    .09862  -1.91442   -.34101

*Fe_MT_BLYP_NLCC.psp   KLEINMAN-BYLANDER
   LMAX=d
   1
   -.04966    .00435   -.91339

&END
===================

Here is part of the output file, the full output file is in the attachment.
===================
 DEGREES OF FREEDOM FOR SYSTEM:                               108

 CPU TIME FOR WAVEFUNCTION INITIALIZATION:         691.99 SECONDS
 ***    RWFOPT| THE NEW SIZE OF THE PROGRAM IS 7276372 KBytes ***
  EWALD| SUM IN REAL SPACE OVER                     1* 1* 1 CELLS

 TOTAL INTEGRATED ELECTRONIC DENSITY
    IN G-SPACE =                                       120.000000
    IN R-SPACE =                                       120.000000
 TOTAL INTEGRATED ABSOLUTE VALUE OF SPIN DENSITY         2.000000

 (K+E1+L+N+X)           TOTAL ENERGY =       106186.37660532 A.U.
 (K)                  KINETIC ENERGY =          170.36965540 A.U.
 (E1=A-S+R)     ELECTROSTATIC ENERGY =            8.41306493 A.U.
 (S)                           ESELF =          164.89614257 A.U.
 (R)                             ESR =            7.57734610 A.U.
 (L)    LOCAL PSEUDOPOTENTIAL ENERGY =       106048.23117170 A.U.
 (N)      N-L PSEUDOPOTENTIAL ENERGY =           19.39264557 A.U.
 (X)     EXCHANGE-CORRELATION ENERGY =          -60.02993229 A.U.
         GRADIENT CORRECTION ENERGY =            -3.00174758 A.U.

 NFI      GEMAX       CNORM           ETOT        DETOT      TCPU
   1  5.789E+00   1.383E-01  106186.376605    0.000E+00    657.40
   2  8.686E+00   1.025E-01   97560.262676   -8.626E+03    625.52
   3  1.089E+01   1.626E-01   91872.833108   -5.687E+03    636.74
   4  9.992E+00   1.349E-01   92811.157892    9.383E+02    640.09
   5  1.136E+01   1.892E-01   89994.894507   -2.816E+03    663.40
   6  2.454E+01   4.955E-01   34606.221165   -5.539E+04    653.28
==================

A longer job (only difference is CUTOFF=70 in that case ) I got something
like this
===================
 NFI      GEMAX       CNORM           ETOT        DETOT      TCPU
   1  2.235E+00   9.835E-02   63037.264963    0.000E+00    315.02
   2  1.926E+00   8.704E-02   60379.229533   -2.658E+03    297.00
   3  2.596E+00   9.187E-02   58256.338687   -2.123E+03    299.82
   4  5.105E+00   1.510E-01   56932.353502   -1.324E+03    302.61
   5  3.417E+00   1.753E-01   55242.431957   -1.690E+03    305.57
   6  3.382E+00   1.303E-01   57670.805897    2.428E+03    308.73
   7  3.528E+00   1.431E-01   59077.167956    1.406E+03    311.61
   8  5.990E+00   3.978E-01   41851.813249   -1.723E+04    314.97
   9  4.477E+00   2.404E-01   54006.746560    1.215E+04    317.90
  10  4.752E+00   2.791E-01   52890.347588   -1.116E+03    320.87
  11  5.294E+00   3.041E-01   52442.000290   -4.483E+02    321.11
 ODIIS| Insufficient progress; reset!
  12  2.027E+00   1.090E-01   57184.733418    4.743E+03    294.10
  13  2.748E+00   1.956E-01   52859.710375   -4.325E+03    297.20
  14  2.175E+00   1.410E-01   54580.632911    1.721E+03    300.05
  15  2.765E+00   1.866E-01   53026.895313   -1.554E+03    303.01
  16  4.017E+00   2.979E-01   48451.018485   -4.576E+03    306.01
  17  3.689E+00   2.535E-01   49096.494350    6.455E+02    309.06
  18  5.621E+00   3.912E-01   39573.558492   -9.523E+03    312.16
  19  2.160E+00   1.421E-01   52656.205961    1.308E+04    314.94
  20  2.746E+00   1.980E-01   50471.977539   -2.184E+03    317.95
  21  2.622E+00   1.947E-01   53253.620361    2.782E+03    321.16
  22  2.326E+00   1.563E-01   52749.439027   -5.042E+02    321.01
  23  3.447E+00   1.939E-01   50260.058884   -2.489E+03    322.45
 ODIIS| Insufficient progress; reset!
  24  3.125E+00   2.316E-01   52263.955271    2.004E+03    298.20
  25  9.174E+00   4.560E-01   28645.700828   -2.362E+04    298.98
  26  6.581E+00   3.604E-01   42865.428348    1.422E+04    302.57
  27  8.131E+00   4.077E-01   36804.591084   -6.061E+03    304.47
  28  8.490E+00   4.228E-01   35472.337851   -1.332E+03    307.96
  29  8.293E+00   4.199E-01   37035.599483    1.563E+03    312.21
  30  8.650E+00   4.403E-01   31113.206639   -5.922E+03    317.06
  31  8.708E+00   4.520E-01   29402.668042   -1.711E+03    335.69
  32  8.714E+00   4.610E-01   31226.023423    1.823E+03    334.76
  33  8.535E+00   4.664E-01   25902.520906   -5.324E+03    342.20
  34  8.569E+00   4.777E-01   24612.360450   -1.290E+03    331.09
 ODIIS| Insufficient progress; reset!
  35  1.186E+01   3.187E-01   -1117.778641   -2.573E+04    300.17
  36  9.641E+00   3.311E-01   -5610.147138   -4.492E+03    303.71
  37  2.563E+00   1.361E-01  -12460.838007   -6.851E+03    306.61
========================

What is wrong in this calculation?
I appreciate your help.

Yong
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