[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
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-------------- 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
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