[molpro-user] Oscillations in CC equations

Ralf Tonner Tonner at chemie.uni-marburg.de
Mon Jun 18 13:19:08 BST 2007


Dear Molpro-Users,

I am using Molpro2006.1 (Patch level 0) on an Opteron-Cluster running under
Linux (Debian) and experience problems with a CCSD(T) calculation.

After successfull HF- and MP2-step the CC equations show oscillative behaviour
and therefore do not converge. 

Is there a way to get rid of these oscillations or does this point to another problem with the calculation?

Any advice is very welcome.

Thank you in advance

Ralf.


-- 
Ralf Tonner
Philipps Universität Marburg
  Fachbereich Chemie
  AK Frenking
Hans-Meerwein-Straße
35032 Marburg
Germany

Tel.: +49-6421/28-27030
Tonner at chemie.uni-marburg.de
------------------------------------------------------------------
INPUT:
memory,800,m

geomtyp=xyz
geometry={
  16

Ni        -0.25384642      0.76651643      1.26150525
C         -0.18413233      0.40166558     -0.49428004
O         -0.08857695      0.20339858     -1.63655314
C          1.28690832      0.30641953      2.05843412
O          2.31725185      0.05098406      2.53426443
C         -1.72337098     -0.42604528      2.05880735
P         -1.69555189     -0.42539188      3.74582260
H         -0.47510329     -0.95359585      4.26597272
H         -2.68259480     -1.20661814      4.45786842
H         -1.76140611      0.79761203      4.52291638
P         -3.17193118     -0.30055559      1.20269108
H         -3.03920016     -0.73727062     -0.15031654
H         -3.82568807      0.97241745      0.96595381
H         -4.31301703     -1.06833006      1.65001920
C         -0.65752128      2.49386056      1.56266147
O         -0.86140466      3.62782720      1.72538688
}

basis={[...]}

hf;
ccsd(t);
-----------------------------------------
OUTPUT:
[...]
 Final occupancy:  56

 !RHF STATE 1.1 ENERGY              -2567.804612994320
 Nuclear energy                       993.07624513
 One-electron energy                -5540.25748214
 Two-electron energy                 1979.37662401
 Virial quotient                       -1.00047711
 !RHF STATE 1.1 DIPOLE MOMENT          -2.21771522    -0.88811812     1.24648844
 Dipole moment /Debye                  -5.63650066    -2.25722325     3.16805008


 **********************************************************************************************************************************
 DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
              1      19        9.59       500      610      700      900      950      970     1000     1100     1400     1410
                                          VAR    BASINP    GEOM    SYMINP    ZMAT    AOBASIS   BASIS      S        T        V
                                         1200     1210     1080     1600      129      960     1650     1700     1800
                                          H0       H01     AOSYM     SMH      P2S    ABASIS   MOLCAS    OPER     GRID

              2       6       12.78       700     1000     1800     1801     2100     2101
                                         GEOM     BASIS    GRID     GRID      RKS      RHF

 PROGRAMS   *        TOTAL        HF        KS       INT
 CPU TIMES  *      1130.45    597.52    352.67    179.98
 REAL TIME  *      2044.67 SEC
 DISK USED  *        34.11 GB
 GA USED    *        78.04 MB       (max)       2.89 MB       (current)
 **********************************************************************************************************************************


1PROGRAM * CCSD (Closed-shell coupled cluster)     Authors: C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992


 Convergence thresholds:  THRVAR = 1.00D-10  THRDEN = 2.24D-06

 CCSD(T)     terms to be evaluated (factor= 1.000)


 Number of core orbitals:          26 (  26 )
 Number of closed-shell orbitals:  30 (  30 )
 Number of external orbitals:     393 ( 393 )

 Setting scratch file implementation to df


 Molecular orbitals read from record     2101.2  Type=RHF/CANONICAL (state 1.1)

 Number of N-1 electron functions:              30
 Number of N-2 electron functions:             465
 Number of singly external CSFs:             11790
 Number of doubly external CSFs:          69507945
 Total number of CSFs:                    69519736

 Length of J-op  integral file:              0.00 MB
 Length of K-op  integral file:             13.87 MB
 Length of 3-ext integral record:            0.00 MB
-10000: WARNING:armci_set_mem_offset: offset changed 0 to 29655040
-10002: WARNING:armci_set_mem_offset: offset changed 0 to 29638656
-10006: WARNING:armci_set_mem_offset: offset changed 0 to 29638656
-10004: WARNING:armci_set_mem_offset: offset changed 0 to 29638656
-10003: WARNING:armci_set_mem_offset: offset changed 0 to 29638656
-10007: WARNING:armci_set_mem_offset: offset changed 0 to 29638656

 For full I/O caching in triples, increase memory by********* words to2133.0 Mword

 Multipassing necessary in transformation. To avoid, increase memory by     758299127 words

 NPASS IN TRSOR3                        2

 Integral transformation finished. Total CPU:2514.04 sec, npass=  3  Memory used: 788.04 MW

 Reference energy:                  -2567.80461299
 MP2 singlet pair energy:              -1.36180661
 MP2 triplet pair energy:              -1.08827428
 MP2 correlation energy:               -2.45008089
 MP2 total energy:                  -2570.25469389

 SCS-MP2 correlation energy:           -2.31131637   (PS=  1.200000  PT=  0.333333)
 SCS-MP2 total energy:              -2570.11592937

 ITER.       NORM       CORR.ENERGY   TOTAL ENERGY   ENERGY CHANGE        DEN1      VAR(S)    VAR(P)  DIIS     TIME
   1      1.77204044    -1.94605584 -2569.75066883     0.50402505    -0.53487635  0.20D+00  0.21D+00  0  0  4083.62
   2      1.93256951    -2.35908415 -2570.16369714    -0.41302831    -0.53850691  0.33D+00  0.19D+00  0  0  5628.79
   3      1.88462152    -2.03066649 -2569.83527948     0.32841766    -0.53324298  0.39D+00  0.15D+00  0  0  7178.40
   4      1.93241434    -2.33147889 -2570.13609188    -0.30081240    -0.52199288  0.41D+00  0.13D+00  0  0  8727.65
   5      1.88679062    -2.05405839 -2569.85867139     0.27742049    -0.49954417  0.39D+00  0.13D+00  0  0 10260.40
   6      1.91770107    -2.32213451 -2570.12674751    -0.26807612    -0.46133074  0.37D+00  0.11D+00  0  0 11796.88
   7      1.88619330    -2.06361580 -2569.86822879     0.25851871    -0.44853256  0.36D+00  0.11D+00  0  0 13356.50
   8      1.91217173    -2.31998783 -2570.12460083    -0.25637204    -0.43037144  0.35D+00  0.11D+00  0  0 14898.12
   9      1.88843206    -2.06668468 -2569.87129767     0.25330315    -0.42674401  0.34D+00  0.11D+00  0  0 16436.74
  10      1.91166660    -2.31992300 -2570.12453599    -0.25323832    -0.42181670  0.34D+00  0.10D+00  0  0 17973.16
  11      1.89081948    -2.06720497 -2569.87181796     0.25271803    -0.42187539  0.34D+00  0.10D+00  0  0 19503.61
  12      1.91260374    -2.32025413 -2570.12486713    -0.25304916    -0.42207812  0.34D+00  0.11D+00  0  0 21035.84
  13      1.89232704    -2.06699631 -2569.87160931     0.25325782    -0.42292876  0.34D+00  0.11D+00  0  0 22559.78
  14      1.91350035    -2.32050999 -2570.12512298    -0.25351368    -0.42419546  0.34D+00  0.11D+00  0  0 24087.59
  15      1.89301875    -2.06674045 -2569.87135345     0.25376954    -0.42483702  0.34D+00  0.11D+00  0  0 25616.42
  16      1.91400930    -2.32063134 -2570.12524434    -0.25389089    -0.42576575  0.34D+00  0.11D+00  0  0 27151.49
  17      1.89324587    -2.06659777 -2569.87121076     0.25403357    -0.42606864  0.34D+00  0.11D+00  0  0 28679.58
  18      1.91421449    -2.32066834 -2570.12528133    -0.25407057    -0.42649639  0.34D+00  0.11D+00  0  0 30203.60
  19      1.89328602    -2.06654735 -2569.87116034     0.25412099    -0.42658830  0.34D+00  0.11D+00  0  0 31728.84
  20      1.91426819    -2.32067114 -2570.12528413    -0.25412379    -0.42671153  0.34D+00  0.11D+00  0  0 33257.68
  21      1.89327898    -2.06654027 -2569.87115327     0.25413086    -0.42671822  0.34D+00  0.11D+00  0  0 34795.40
  22      1.91427048    -2.32066625 -2570.12527925    -0.25412598    -0.42672176  0.34D+00  0.11D+00  0  0 36320.14
  23      1.89327224    -2.06654538 -2569.87115838     0.25412087    -0.42670948  0.34D+00  0.11D+00  0  0 37837.94
  24      1.91426458    -2.32066264 -2570.12527563    -0.25411726    -0.42668845  0.34D+00  0.11D+00  0  0 39370.54
  25      1.89327290    -2.06655032 -2569.87116331     0.25411232    -0.42667947  0.34D+00  0.11D+00  0  0 40900.25
  26      1.91426204    -2.32066136 -2570.12527435    -0.25411104    -0.42666484  0.34D+00  0.11D+00  0  0 42424.96
  27      1.89327726    -2.06655266 -2569.87116565     0.25410870    -0.42666173  0.34D+00  0.11D+00  0  0 43960.19
  28      1.91426277    -2.32066137 -2570.12527436    -0.25410871    -0.42665638  0.34D+00  0.11D+00  0  0 45489.30
  29      1.89328179    -2.06655320 -2569.87116620     0.25410816    -0.42665652  0.34D+00  0.11D+00  0  0 47012.66
  30      1.91426466    -2.32066176 -2570.12527476    -0.25410856    -0.42665622  0.34D+00  0.11D+00  0  0 48542.79
  31      1.89328508    -2.06655304 -2569.87116604     0.25410872    -0.42665729  0.34D+00  0.11D+00  0  0 50076.30
  32      1.91426638    -2.32066211 -2570.12527510    -0.25410906    -0.42665852  0.34D+00  0.11D+00  0  0 51619.92
  33      1.89328708    -2.06655277 -2569.87116577     0.25410934    -0.42665945  0.34D+00  0.11D+00  0  0 53140.57
  34      1.91426753    -2.32066232 -2570.12527531    -0.25410955    -0.42666059  0.34D+00  0.11D+00  0  0 54681.26
  35      1.89328818    -2.06655259 -2569.87116558     0.25410973    -0.42666116  0.34D+00  0.11D+00  0  0 56210.33
  36      1.91426820    -2.32066242 -2570.12527542    -0.25410984    -0.42666185  0.34D+00  0.11D+00  0  0 57731.10
  37      1.89328877    -2.06655249 -2569.87116549     0.25410993    -0.42666213  0.34D+00  0.11D+00  0  0 59254.48
  38      1.91426856    -2.32066247 -2570.12527546    -0.25410997    -0.42666246  0.34D+00  0.11D+00  0  0 60787.01
  39      1.89328910    -2.06655246 -2569.87116545     0.25411001    -0.42666259  0.34D+00  0.11D+00  0  0 62313.06

 Norm of t1 vector:      0.23394838      S-energy:     0.00003517      T1 diagnostic:  0.04415393
                                                                       D1 diagnostic:  0.16324488
 Norm of t2 vector:      0.65934072      P-energy:    -2.06658763

 ?CONVERGENCE NOT REACHED AFTER MAX. ITERATIONS

 ?ERROR: NO CONVERGENCE. TRIPLES WILL NOT BE DONE. THIS CAN BE AVOIDED USING THE NOCHECK OPTION.

 RESULTS
 =======

 CCSD singlet pair energy              -1.326800872878
 CCSD triplet pair energy              -0.739786753905


 Reference energy                   -2567.804612994315
 Correlation energy                    -2.066552457636

 !CCSD STATE 1.1 ENERGY             -2569.871165451951

 Program statistics:

 Available memory in ccsd:               799997200
 Min. memory needed in ccsd:             157814551
 Max. memory used in ccsd:               223597096
 Max. memory used in cckext:             190149716 (39 integral passes)


 ? Error
 ? No convergence. This error exit can be avoided using the NOCHECK option
 ? The problem occurs in ccsd

 GA ERROR fehler on processor   0






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