[molpro-user] problem in CPHF

Moilanen Jani jani.o.moilanen at jyu.fi
Fri Nov 15 13:53:07 GMT 2013


Dear Molpro users

I have already asked this question, but I did not get respond so I decided to send it again.  I would highly appreciate if someone could help.

I try to optimize the geometry of the copper complex of selenium diimide at the QCISD/def2-TZVP (def2-TZVPP for Cu) and QCISD(T)/def2-TZVP (def2-TZVPP for Cu) levels of theory. If I use the largest plausible noble gas core in calculations, they convergence properly. However, if I try to include 3s and 3p electrons of copper atoms into to the correlation space, i.e. I use slightly smaller frozen core, the CPHF does not convergence anymore ( I included input and part of the output below). Please, can anyone help me with this problem?

Best wishes,

Jani

Input:
***,qsicd,def2-TZVP
memory,465,m
gprint,orbitals
geomtyp=xyz
geometry={
 N          2.3292993475       -0.3193490423        0.0000000000
 Se         2.2252015172       -2.0236429889        0.0000000000
 N          0.5383403946       -2.2881665746        0.0000000000
 Cu        -0.8987236544       -0.9879670894        0.0000000000
 N         -2.3292993475        0.3193490423        0.0000000000
 Se        -2.2252015172        2.0236429889        0.0000000000
 N         -0.5383403946        2.2881665746        0.0000000000
 Cu         0.8987236544        0.9879670894        0.0000000000
 H         -0.3496985521        3.3008960282        0.0000000000
 H          3.3196724011       -0.0358505140        0.0000000000
 H          0.3496985521       -3.3008960282        0.0000000000
 H         -3.3196724011        0.0358505140        0.0000000000

}

basis={

default=def2-TZVP,Cu=def2-TZVPP

}

{hf;wf,156,1,0;orbprint,2}

{qcisd,maxit=80;core,13,3,13,3;natorb,5000.2,10}

optg

{put,molden,sc_qcisd.molden;orbital,5000.2}

Output:

 ITER   MIC  DIIS      VAR         VARC       CPU
   1     0     1    0.36D+00    0.10D-01     0.58
   2    10     0    0.75D+01    0.39D-01     1.51
   3    10     0    0.16D+03    0.80D+00     2.26
   4    10     0    0.32D+04    0.17D+02     3.02
   5    10     0    0.67D+05    0.34D+03     3.77
   6    10     0    0.14D+07    0.71D+04     4.52
   7    10     0    0.29D+08    0.15D+06     5.28
   8    10     0    0.60D+09    0.31D+07     6.03
   9    10     0    0.12D+11    0.63D+08     6.78
  10    10     0    0.26D+12    0.13D+10     7.54
  11    10     0    0.53D+13    0.27D+11     8.29
  12    10     0    0.11D+15    0.56D+12     9.04
  13    10     0    0.23D+16    0.12D+14     9.79
  14    10     0    0.48D+17    0.24D+15    10.54
  15    10     0    0.99D+18    0.50D+16    11.29
  16    10     0    0.20D+20    0.10D+18    12.05
  17    10     0    0.42D+21    0.22D+19    12.80
  18    10     0    0.88D+22    0.45D+20    13.54
  19    10     0    0.18D+24    0.93D+21    14.30
  20    10     0    0.38D+25    0.19D+23    15.05
  21    10     0    0.78D+26    0.40D+24    15.83
  22    10     0    0.16D+28    0.83D+25    16.59
  23    10     0    0.34D+29    0.17D+27    17.33
  24    10     0    0.70D+30    0.35D+28    18.07
  25    10     0    0.14D+32    0.74D+29    18.80
  26    10     0    0.30D+33    0.15D+31    19.55
  27    10     0    0.62D+34    0.32D+32    20.30
  28    10     0    0.13D+36    0.65D+33    21.05
  29    10     0    0.27D+37    0.14D+35    21.78
  30    10     0    0.55D+38    0.28D+36    22.53
  31    10     0    0.11D+40    0.58D+37    23.27
  32    10     0    0.24D+41    0.12D+39    24.02
  33    10     0    0.49D+42    0.25D+40    24.77
  34    10     0    0.10D+44    0.52D+41    25.52
  35    10     0    0.21D+45    0.11D+43    26.28
  36    10     0    0.44D+46    0.22D+44    27.03
  37    10     0    0.91D+47    0.46D+45    27.79
  38    10     0    0.19D+49    0.96D+46    28.55
  39    10     0    0.39D+50    0.20D+48    29.31
  40    10     0    0.81D+51    0.41D+49    30.06
  41    10     0    0.17D+53    0.85D+50    30.81
  42    10     0    0.35D+54    0.18D+52    31.57
  43    10     0    0.72D+55    0.37D+53    32.31
  44    10     0    0.15D+57    0.76D+54    33.05
  45    10     0    0.31D+58    0.16D+56    33.80
  46    10     0    0.64D+59    0.33D+57    34.55

 No convergence of CPHF after  46 macroiterations and  454 microiterations.   Accuracy: 1.4683D+59

 ?ERROR: NO CONVERGENCE. EXIT FROM CPHF THIS CAN BE AVOIDED USING THE NOCHECK OPTION.
B



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