CI CONVERGENGE PROBLEM

Apostolos Kalemos kalemos at chem.uoa.gr
Mon Aug 6 13:51:02 BST 2001


Dear sir,

I am working on the SiH molecular system using an
aug-cc-pV6Z basis set for the Si atom and a cc-pV5Z
for H. I am interested in obtaining states of 2P and of 2S+
molecular symmetry and of Rydberg character.These are the
3rd and 4th roots of the 2B1 symmetry block (in the case of
the 2P states) while for the 2S+ states two states of 2D symmetry
increase the number of roots in the 2A1 block to six (instead of 4).

    At the CI level there are some oscillatory problems, with either the

project method or the traditional way of performing the CI, which make
impossible the calculation of these higher roots.A sample of my output
is
the following

*******In the case of the 2B1 states:

ITER. STATE  ROOT      NORM       CORR.ENERGY   TOTAL ENERGY   ENERGY
CHANGE       DEN1      VAR(S)    VAR(P)      TIME
    1     1     1     1.00000000     0.00000000  -289.49852042
0.00000000    -0.02764999  0.94D-02  0.20D-02  1054.67
    1     2     2     1.00000000     0.00000000  -289.31967006
0.00000000    -0.02775066  0.13D-01  0.18D-02  1054.67
    1     3     3     1.00000000     0.00000000  -289.25943623
0.00000000    -0.02379833  0.11D-01  0.16D-02  1054.67
    1     4     4     1.00000000     0.00000000  -289.24523446
0.00000000    -0.02417010  0.11D-01  0.16D-02  1054.67

 GPQ1:   4 BATCHES OF G-OPERATORS PROCESSED

    2     1     1     1.01433878    -0.03092157  -289.52944199
-0.03092157    -0.00120274  0.22D-03  0.18D-03 16158.92
    2     2     2     1.01819489    -0.03108957  -289.35075963
-0.03108957    -0.00153608  0.61D-03  0.17D-03 16158.92
    2     3     3     1.01754783    -0.02767075  -289.28710698
-0.02767075    -0.00177771  0.89D-03  0.19D-03 16158.92
    2     4     4     1.01721942    -0.02785210  -289.27308655
-0.02785210    -0.00150471  0.76D-03  0.18D-03 16158.92
    3     1     1     1.01720785    -0.03247121  -289.53099163
-0.00154964    -0.00012322  0.30D-04  0.17D-04 31220.32
    3     2     2     1.02481909    -0.03321994  -289.35289000
-0.00213037    -0.00027419  0.19D-03  0.23D-04 31220.32
    3     3     3     1.02740102    -0.03065364  -289.29008987
-0.00298289    -0.00083818  0.79D-03  0.55D-04 31220.32
    3     4     4     1.02574216    -0.03010446  -289.27533892
-0.00225236    -0.00041099  0.37D-03  0.33D-04 31220.32
    4     1     1     1.01801863    -0.03262053  -289.53114095
-0.00014932    -0.00001538  0.31D-05  0.23D-05 46324.23
    4     2     2     1.02955580    -0.03363353  -289.35330359
-0.00041359    -0.00008552  0.50D-04  0.74D-05 46324.23
    4     3     3     1.06448106    -0.03343642  -289.29287265
-0.00278278    -0.00183745  0.12D-02  0.16D-03 46324.23
    4     4     4     1.03717449    -0.03089536  -289.27612981
-0.00079090    -0.00028088  0.19D-03  0.26D-04 46324.23
    5     1     1     1.01808184    -0.03263880  -289.53115922
-0.00001827    -0.00000204  0.37D-06  0.33D-06 61398.65
    5     2     2     1.03137196    -0.03375352  -289.35342358
-0.00011999    -0.00002555  0.14D-04  0.23D-05 61398.65
    5     3     3     1.12110991    -0.03718917  -289.29662540
-0.00375275    -0.00196139  0.11D-02  0.17D-03 61398.65
    5     4     4     1.04567125    -0.03141293  -289.27664739
-0.00051758    -0.00023078  0.13D-03  0.21D-04 61398.65
    6     1     1     1.01810127    -0.03264119  -289.53116161
-0.00000239    -0.00000034  0.60D-07  0.57D-07 76510.95
    6     2     2     1.03236713    -0.03378679  -289.35345685
-0.00003327    -0.00000755  0.43D-05  0.67D-06 76510.95
    6     3     3     1.19854965    -0.04044042  -289.29987664
-0.00325124    -0.00130208  0.75D-03  0.12D-03 76510.95
    6     4     4     1.05249199    -0.03180415  -289.27703860
-0.00039121    -0.00020566  0.13D-03  0.19D-04 76510.95
    7     1     1     1.01812107    -0.03264160  -289.53116202
-0.00000041    -0.00000006  0.11D-07  0.11D-07 91606.57
    7     2     2     1.03305901    -0.03379696  -289.35346702
-0.00001017    -0.00000262  0.15D-05  0.21D-06 91606.57
    7     3     5     1.13347364    -0.00623017  -289.26566640
0.03421024    -0.01737878  0.89D-02  0.15D-02 91606.57
    7     4     4     1.07068219    -0.03251439  -289.27774884
-0.00071024    -0.00088751  0.47D-03  0.78D-04 91606.57
    8     1     1     1.01812397    -0.03264167  -289.53116209
-0.00000007    -0.00000001  0.23D-08  0.22D-08106717.13
    8     2     2     1.03332270    -0.03380026  -289.35347032
-0.00000330    -0.00000088  0.55D-06  0.68D-07106717.13
    8     3     5     1.07889738    -0.00607870  -289.26551492
0.00015148    -0.03222493  0.16D-01  0.21D-02106717.13
    8     4     4     1.05177145    -0.03130259  -289.27653705
0.00121180    -0.00060504  0.31D-03  0.45D-04106717.13
    9     1     1     1.01812416    -0.03264167  -289.53116210
0.00000000    -0.00000001  0.23D-08  0.22D-08119708.23
    9     2     2     1.03341684    -0.03380131  -289.35347137
-0.00000105    -0.00000032  0.21D-06  0.23D-07119708.23
    9     3     4     1.13064238    -0.02023358  -289.27966981
-0.01415489    -0.00623864  0.24D-02  0.60D-03119708.23
    9     4     5     1.04892436    -0.03114716  -289.27638162
0.00015543    -0.00016694  0.74D-04  0.17D-04119708.23
   10     1     1     1.01812418    -0.03264167  -289.53116210
0.00000000    -0.00000001  0.23D-08  0.22D-08132699.73
   10     2     2     1.03350680    -0.03380172  -289.35347178
-0.00000041    -0.00000015  0.10D-06  0.10D-07132699.73
   10     3     4     1.16027856    -0.01919037  -289.27862660
0.00104321    -0.01683630  0.77D-02  0.17D-02132699.73
   10     4     5     1.05174415    -0.03123047  -289.27646493
-0.00008331    -0.00001238  0.87D-05  0.12D-05132699.73
   11     1     1     1.01812439    -0.03264167  -289.53116210
0.00000000    -0.00000001  0.22D-08  0.22D-08145936.88
   11     2     2     1.03357123    -0.03380191  -289.35347197
-0.00000019    -0.00000007  0.49D-07  0.49D-08145936.88
   11     3     5     1.09226379     0.00434927  -289.25508696
0.02353964    -0.02822291  0.13D-01  0.19D-02145936.88
   11     4     4     1.05341271    -0.03124916  -289.27648361
-0.00001868    -0.00000717  0.47D-05  0.60D-06145936.88


*****In the case of the 2A1 states

 ITER. STATE  ROOT      NORM       CORR.ENERGY   TOTAL ENERGY   ENERGY
CHANGE       DEN1      VAR(S)    VAR(P)      TIME
    1     1     6     1.00000000     0.00000000  -289.21030839
0.00000000    -0.03094616  0.14D-01  0.30D-02   204.68
    2     1     6     1.02220453    -0.03561498  -289.24592337
-0.03561498    -0.00246448  0.17D-02  0.26D-03  1421.84
    3     1     6     1.04507088    -0.04032655  -289.25063494
-0.00471157    -0.00155849  0.20D-02  0.12D-03  2616.44
    4     1     6     1.20751866    -0.04711402  -289.25742240
-0.00678747    -0.00520467  0.61D-02  0.41D-03  3858.93
    5     1     7     1.12753931    -0.03238077  -289.24268916
0.01473325    -0.00479783  0.71D-02  0.29D-03  5162.34
    6     1     7     1.03846171    -0.02692988  -289.23723827
0.00545088    -0.00843053  0.62D-02  0.10D-02  6515.73
    7     1     6     1.21185148    -0.04567927  -289.25598766
-0.01874938    -0.00879992  0.93D-02  0.80D-03  7849.84
 Denominator 1c22000000000000                   AOrb=  1Den
(unshifted)=    0.1843
    8     1     7     1.20760402     0.00312528  -289.20718311
0.04880455    -0.04414078  0.58D-01  0.30D-02  9176.60
    9     1     7     1.06983578    -0.01591899  -289.22622738
-0.01904427    -0.03248775  0.19D-01  0.34D-02 10525.92
   10     1     7     1.08231807    -0.03316201  -289.24347040
-0.01724302    -0.00339384  0.35D-02  0.23D-03 11889.01
   11     1     7     1.47180942    -0.01261918  -289.22292757
0.02054283    -0.04251522  0.43D-01  0.50D-02 13242.01
   12     1     7     1.02589777    -0.03361032  -289.24391870
-0.02099113    -0.00293806  0.27D-02  0.15D-03 14586.69
   13     1     6     1.05092239    -0.03839943  -289.24870781
-0.00478911    -0.00080289  0.58D-03  0.83D-04 15938.06
   14     1     6     1.06174993    -0.03976244  -289.25007083
-0.00136302    -0.00057309  0.60D-03  0.37D-04 17298.33
   15     1     6     1.08031831    -0.04086986  -289.25117824
-0.00110741    -0.00041060  0.41D-03  0.32D-04 18651.48
   16     1     6     1.09254858    -0.04166859  -289.25197697
-0.00079873    -0.00080338  0.12D-02  0.31D-04 19967.20
   17     1     7     1.64093601    -0.03081394  -289.24112232
0.01085465    -0.02791623  0.22D-01  0.29D-02 21272.58
 Denominator 1c22000000000000                   AOrb=  1Den
(unshifted)=    0.1954
   18     1     7     1.02915560    -0.00795707  -289.21826546
0.02285686    -0.03609556  0.26D-01  0.29D-02 22566.02
   19     1     6     1.26757687    -0.05155008  -289.26185847
-0.04359301    -0.00881198  0.77D-02  0.68D-03 23909.77
   20     1     7     1.10745084    -0.01736312  -289.22767151
0.03418696    -0.02491111  0.43D-01  0.16D-02 25245.63
   21     1     7     1.03858641    -0.03311457  -289.24342296
-0.01575145    -0.00283130  0.24D-02  0.25D-03 26589.32
   22     1     6     1.06764920    -0.03770653  -289.24801492
-0.00459196    -0.00106471  0.93D-03  0.79D-04 27936.41
   23     1     6     1.12520495    -0.04010023  -289.25040861
-0.00239369    -0.00109856  0.12D-02  0.88D-04 29279.03
   24     1     6     1.24703577    -0.04256636  -289.25287474
-0.00246613    -0.00149389  0.21D-02  0.96D-04 30647.51
   25     1     7     1.12642115    -0.03275260  -289.24306098
0.00981376    -0.01580149  0.12D-01  0.98D-03 32032.19
   26     1     6     1.39423970    -0.05365906  -289.26396744
-0.02090646    -0.01226527  0.11D-01  0.10D-02 33393.54
 Denominator 1c22000000000000                   AOrb=  1Den
(unshifted)=    0.1880
   27     1     7     1.13623648    -0.00059385  -289.21090224
0.05306521    -0.04151603  0.47D-01  0.31D-02 34739.69
   28     1     7     1.01666668    -0.02652342  -289.23683181
-0.02592957    -0.00964246  0.62D-02  0.93D-03 36089.32
   29     1     7     1.04898788    -0.03604619  -289.24635457
-0.00952277    -0.00159088  0.15D-02  0.11D-03 37451.99


I would very much appreciate any kind of suggestion.

Sincerely yours,
Apostolos KALEMOS

--
Apostolos Kalemos
National and Kapodistrian University of Athens
Department of Chemistry
Laboratory of Physical Chemistry
PO Box 64004, 157 10 Zografou
Athens-Greece
---
tel :+(301)7274569
fax :+(301)7274752
e-mail :kalemos at chem.uoa.gr

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