[molpro-user] problem in CPHF

Moilanen Jani jani.o.moilanen at jyu.fi
Tue Nov 19 07:23:49 GMT 2013


Dear Kirk and Yinan

Thank you for the comments and input. The level shift fixed the convergence problem: CPHF convergences now nicely.

Best regards,

Jani

________________________________
Lähettäjä: Shu Yinan [ben.vival at gmail.com]
Lähetetty: 15. marraskuuta 2013 19:00
Vastaanottaja: Moilanen Jani
Kopio: molpro-user at molpro.net
Aihe: Re: [molpro-user] problem in CPHF

Dear Jani,

You could add shift for the cphf to make it converge.

I would try cphf,shift=0.3 under the qcisd command.

If 0.3 doesn't work, try 0.5. But usually it should be enough.

Best,

Yinan Shu
Ph.D. student
Department of Chemistry
Chemistry Building, Room 220A
Michigan State University
East Lansing, MI48824
517-580-9908



On 2013-11-15, at 上午11:53, Shu Yinan <shuyinan at msu.edu<mailto:shuyinan at msu.edu>> wrote:

Dear Jani,

You could add shift for the cphf to make it converge.

I would try  add  cphf, shift=0.3 under the qcisd command.

If 0.3 still doesn't work, try 0.5.

But usually 0.3 should be enough.


Yinan Shu
Ph.D. student
Department of Chemistry
Chemistry Building, Room 220A
Michigan State University
East Lansing, MI48824
517-580-9908






On 2013-11-15, at 上午8:53, Moilanen Jani <jani.o.moilanen at jyu.fi<mailto:jani.o.moilanen at jyu.fi>> wrote:

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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