[molpro-user] ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL

Wolfgang Eisfeld wolfgang.eisfeld at ch.tum.de
Mon Jul 11 12:48:51 BST 2005


Dear molpro-users,

I'm facing a strange problem in some large MRCI calculations. You can find
an example part of the output in the attachment. The important line
reads:

 ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL STATE=1 EIG=
-145.33053898 EXPECT.= -145.33256100

Apparently, something is going wrong in the CI calculation but I cannot
figure out what. Does anybody know something about this problem,
particularly how to solve it?

Best regards,

Wolfgang

-------------------------------------------------------------------------------
Dr. Wolfgang Eisfeld
Technical University Munich  -  Chair of Theoretical Chemistry
Lichtenbergstr. 4            -  D-85747 Garching, Germany
Phone: +49-89-289 13 614
Fax:   +49-89-289 13 622     -  e-mail: wolfgang.eisfeld at ch.tum.de
-------------------------------------------------------------------------------

-------------- next part --------------
1PROGRAM * CI (Multireference internally contracted CI)     Authors: H.-J. Werner, P.J. Knowles, 1987


 Configurations given as data for symmetry 1

   1   2020122000                      
   2   2021022000                      
   3   2100022200                      
   4   2120012100                      
   5   2200120002                      
   6   2200120200                      
   7   2200121100                      
   8   2200122000                      
   9   2201020002                      
  10   2201020200                      
  11   2201021100                      
  12   2201022000                      
  13   2210002200                      
  14   2210012100                      
  15   2210020002                      
  16   2210020101                      
  17   2210020200                      
  18   2210021100                      
  19   2210022000                      

 Configurations given as data for symmetry 2

   1   22222222220200221200            
   2   22222222220200222010            
   3   22222222220200222100            
   4   22222222222000202210            
   5   22222222222000212200            
   6   22222222222000220012            
   7   22222222222000220102            
   8   22222222222000220111            
   9   22222222222000220201            
  10   22222222222000220210            
  11   22222222222000221002            
  12   22222222222000221011            
  13   22222222222000221101            
  14   22222222222000221110            
  15   22222222222000221200            
  16   22222222222000222001            
  17   22222222222000222010            
  18   22222222222000222100            

 Convergence thresholds:  THRVAR = 1.00D-08  THRDEN = 1.00D-06

 Number of optimized states:  3  Roots:   1   2   3
 Number of reference states:  3  Roots:   1   2   3

 Reference symmetries:    1   2

 Reference symmetry:               1   Doublet 
 Maximum shell inside CICON        9

 Maximum number of shells reduced from  9 to  5
 Maximum number of spin couplings:     42

 Reference space:       19 conf       25 CSFs
 N elec internal:    31377 conf   126289 CSFs
 N-1 el internal:    13455 conf    73134 CSFs
 N-2 el internal:     3688 conf    23924 CSFs

 Number of electrons in valence space:                     29
 Maximum number of open shell orbitals in reference space:  3
 Maximum number of open shell orbitals in internal spaces:  9


 Number of core orbitals:           3 (   3   0 )
 Number of closed-shell orbitals:  10 (   9   1 )
 Number of active  orbitals:       10 (   5   5 )
 Number of external orbitals:     264 ( 171  93 )
 
 Molecular orbitals read from record     2140.2  Type=MCSCF/NATURAL (state averaged)

 Coulomb and exchange operators available. No transformation done.

 Number of p-space configurations:  14

 Reference wavefunction optimized for reference space (refopt=1)

 State     Reference Energy 
   1        -144.71567637
   2        -144.70207303
   3        -144.69653290

 ?WARNING: SMALL EIGENVALUE OF PAIR OVERLAP MATRIX:  0.4303D-06

 ?WARNING: SMALL EIGENVALUE OF PAIR OVERLAP MATRIX:  0.1414D-06

 ?WARNING: SMALL EIGENVALUE OF PAIR OVERLAP MATRIX:  0.1183D-06

 Number of blocks in overlap matrix:   412   Smallest eigenvalue:  0.12D-06
 Number of N-2 electron functions:    1011
 Number of N-1 electron functions:   73134

 Number of internal configurations:                61479
 Number of singly external configurations:       9549558
 Number of doubly external configurations:      17988561
 Total number of contracted configurations:     27599598
 Total number of uncontracted configurations:  427234377

 Diagonal Coupling coefficients finished.               Storage:26992650 words, CPU-Time:     33.21 seconds.
 Energy denominators for pairs finished in 1 passes.    Storage: 5965029 words, CPU-time:     11.02 seconds.

  ITER. STATE  ROOT      NORM       CORR.ENERGY   TOTAL ENERGY   ENERGY CHANGE       DEN1      VAR(S)    VAR(P)      TIME
    1     1     1     1.00000000     0.00000000  -144.71567637     0.00000000    -0.68027010  0.28D-01  0.20D+00   233.03
    1     2     2     1.00000000     0.00000000  -144.70207303     0.00000000    -0.78705135  0.68D-01  0.22D+00   233.03
    1     3     3     1.00000000     0.00000000  -144.69653290     0.00000000    -0.69126764  0.33D-01  0.20D+00   233.03
    2     1     2     1.17334653    -0.61688463  -145.33053898    -0.61486261    -0.01263658  0.20D-02  0.21D-02  2068.75

 ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL STATE=1  EIG=  -145.33053898  EXPECT.=  -145.33256100
    2     2     1     1.19180319    -0.65043351  -145.34209529    -0.64002225    -0.01896985  0.44D-02  0.26D-02  2068.75

 ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL STATE=2  EIG=  -145.34209529  EXPECT.=  -145.35250654
    2     3     3     1.17361074    -0.62081834  -145.31463151    -0.61809861    -0.01300484  0.22D-02  0.21D-02  2068.75

 ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL STATE=3  EIG=  -145.31463151  EXPECT.=  -145.31735124
    3     1     2     1.17230180    -0.62034116  -145.33172776    -0.00118877    -0.00650827  0.95D-03  0.11D-02  4281.37

 ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL STATE=1  EIG=  -145.33172776  EXPECT.=  -145.33601753
    3     2     1     1.18845338    -0.66474423  -145.35238941    -0.01029412    -0.00186932  0.23D-03  0.34D-03  4281.37

 ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL STATE=2  EIG=  -145.35238941  EXPECT.=  -145.36681726
    3     3     3     1.17308414    -0.62490088  -145.31588904    -0.00125753    -0.00635039  0.96D-03  0.11D-02  4281.37

 ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL STATE=3  EIG=  -145.31588904  EXPECT.=  -145.32143377
    4     1     2     1.17409126    -0.62098330  -145.33254758    -0.00081982    -0.00698173  0.14D-02  0.10D-02  6483.71

 ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL STATE=1  EIG=  -145.33254758  EXPECT.=  -145.33665967
    4     2     1     1.18851388    -0.66510739  -145.35258175    -0.00019234    -0.00152819  0.24D-03  0.26D-03  6483.71

 ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL STATE=2  EIG=  -145.35258175  EXPECT.=  -145.36718043
    4     3     3     1.17438478    -0.62538903  -145.31634091    -0.00045187    -0.00651748  0.13D-02  0.97D-03  6483.71

 ?EXPECTATION VALUE AND EIGENVALUE NOT IDENTICAL STATE=3  EIG=  -145.31634091  EXPECT.=  -145.32192193


More information about the Molpro-user mailing list