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Z vector equation error constant throughout iterations #208

Closed nagb closed 4 years ago

nagb commented 4 years ago

I don't know if this has come up to any users before but I couldn't find anything while searching through the archive in here.

I am running an MS-CASPT2 optimisation and while the program is going through the gradient stage it gets stuck trying to solve the Z vector equations:

=== CASSCF Z-vector iteration ===

     0      0.0037950075   151.7911993374      1.64
- linear dependency detected:    1 /    2    min eigenvalue:     9.6233e-09    max eigenvalue:     9.6233e-09
* Using canonical orthogonalization due to linear dependency

     1      0.0038000891   151.7911995828      1.46
- linear dependency detected:    2 /    3    min eigenvalue:    -3.9371e-16    max eigenvalue:     7.1625e-09
* Using canonical orthogonalization due to linear dependency

     2      0.0038091857   151.7911997637      1.67
- linear dependency detected:    3 /    4    min eigenvalue:    -2.6138e-16    max eigenvalue:     2.6369e-09
* Using canonical orthogonalization due to linear dependency

     3      0.0038157240   151.7911997210      1.78
- linear dependency detected:    4 /    5    min eigenvalue:    -9.5739e-17    max eigenvalue:     5.2881e-09
* Using canonical orthogonalization due to linear dependency

     4      0.0038124812   151.7911997586      1.62
- linear dependency detected:    5 /    6    min eigenvalue:    -5.8490e-16    max eigenvalue:     6.2254e-09
* Using canonical orthogonalization due to linear dependency

     5      0.0038104955   151.7911997658      1.52
- linear dependency detected:    6 /    7    min eigenvalue:    -2.6349e-16    max eigenvalue:     6.5097e-09
* Using canonical orthogonalization due to linear dependency

     6      0.0038095331   151.7911997648      1.49
- linear dependency detected:    7 /    8    min eigenvalue:    -3.1906e-16    max eigenvalue:     6.6177e-09
* Using canonical orthogonalization due to linear dependency

     7      0.0038090163   151.7911997630      1.48
- linear dependency detected:    8 /    9    min eigenvalue:    -8.8894e-16    max eigenvalue:     6.6659e-09
* Using canonical orthogonalization due to linear dependency

     8      0.0038087188   151.7911997616      1.50
- linear dependency detected:    9 /   10    min eigenvalue:    -2.4152e-15    max eigenvalue:     6.6901e-09
* Using canonical orthogonalization due to linear dependency

     9      0.0038085355   151.7911997606      1.54
- linear dependency detected:   10 /   11    min eigenvalue:    -6.2078e-16    max eigenvalue:     6.7035e-09
* Using canonical orthogonalization due to linear dependency

    10      0.0038084156   151.7911997598      1.50
- linear dependency detected:   11 /   12    min eigenvalue:    -1.0187e-15    max eigenvalue:     6.7114e-09
* Using canonical orthogonalization due to linear dependency

    11      0.0038083332   151.7911997593      1.76
- linear dependency detected:   12 /   13    min eigenvalue:    -1.1373e-15    max eigenvalue:     6.7164e-09
* Using canonical orthogonalization due to linear dependency

    12      0.0038082743   151.7911997589      1.77
- linear dependency detected:   13 /   14    min eigenvalue:    -5.9847e-16    max eigenvalue:     6.7196e-09
* Using canonical orthogonalization due to linear dependency

    13      0.0038082308   151.7911997586      1.56
- linear dependency detected:   14 /   15    min eigenvalue:    -1.1299e-15    max eigenvalue:     6.7218e-09
* Using canonical orthogonalization due to linear dependency

    14      0.0038081978   151.7911997584      1.53
- linear dependency detected:   15 /   16    min eigenvalue:    -2.1309e-15    max eigenvalue:     6.7233e-09
* Using canonical orthogonalization due to linear dependency

    15      0.0038081722   151.7911997582      1.60
- linear dependency detected:   16 /   17    min eigenvalue:    -2.7386e-15    max eigenvalue:     6.7244e-09
* Using canonical orthogonalization due to linear dependency

    16      0.0038081520   151.7911997581      1.88
- linear dependency detected:   17 /   18    min eigenvalue:    -1.6310e-15    max eigenvalue:     6.7252e-09
* Using canonical orthogonalization due to linear dependency

    17      0.0038081357   151.7911997579      1.59
- linear dependency detected:   18 /   19    min eigenvalue:    -2.0190e-15    max eigenvalue:     6.7258e-09
* Using canonical orthogonalization due to linear dependency

    18      0.0038081225   151.7911997578      1.73
- linear dependency detected:   19 /   20    min eigenvalue:    -2.1896e-15    max eigenvalue:     6.7263e-09
* Using canonical orthogonalization due to linear dependency

    19      0.0038081116   151.7911997578      1.58
- linear dependency detected:   20 /   21    min eigenvalue:    -4.5704e-15    max eigenvalue:     6.7267e-09
* Using canonical orthogonalization due to linear dependency

    20      0.0038081026   151.7911997577      1.44
- linear dependency detected:   21 /   22    min eigenvalue:    -4.2884e-15    max eigenvalue:     6.7269e-09
* Using canonical orthogonalization due to linear dependency

    21      0.0038080949   151.7911997576      1.54
- linear dependency detected:   22 /   23    min eigenvalue:    -1.3493e-15    max eigenvalue:     6.7272e-09
* Using canonical orthogonalization due to linear dependency

    22      0.0038080884   151.7911997576      1.50
- linear dependency detected:   23 /   24    min eigenvalue:    -1.4167e-15    max eigenvalue:     6.7273e-09
* Using canonical orthogonalization due to linear dependency

    23      0.0038080829   151.7911997576      1.45
- linear dependency detected:   24 /   25    min eigenvalue:    -1.2044e-15    max eigenvalue:     6.7275e-09
* Using canonical orthogonalization due to linear dependency

    24      0.0038080781   151.7911997575      1.44
- linear dependency detected:   25 /   26    min eigenvalue:    -1.4839e-15    max eigenvalue:     6.7276e-09
* Using canonical orthogonalization due to linear dependency

    25      0.0038080740   151.7911997575      1.45
- linear dependency detected:   26 /   27    min eigenvalue:    -6.0602e-15    max eigenvalue:     6.7277e-09
* Using canonical orthogonalization due to linear dependency

    26      0.0038080703   151.7911997575      1.52
- linear dependency detected:   27 /   28    min eigenvalue:    -1.2136e-15    max eigenvalue:     6.7278e-09
* Using canonical orthogonalization due to linear dependency

    27      0.0038080672   151.7911997574      1.48
- linear dependency detected:   28 /   29    min eigenvalue:    -3.5270e-15    max eigenvalue:     6.7278e-09
* Using canonical orthogonalization due to linear dependency

    28      0.0038080644   151.7911997574      1.53
- linear dependency detected:   29 /   30    min eigenvalue:    -1.6051e-15    max eigenvalue:     6.7279e-09
* Using canonical orthogonalization due to linear dependency

    29      0.0038080619   151.7911997574      1.43
- linear dependency detected:   30 /   31    min eigenvalue:    -3.2801e-15    max eigenvalue:     6.7280e-09
* Using canonical orthogonalization due to linear dependency

    30      0.0038080597   151.7911997574      1.51
- linear dependency detected:   31 /   32    min eigenvalue:    -1.3774e-15    max eigenvalue:     6.7280e-09
* Using canonical orthogonalization due to linear dependency

    31      0.0038080577   151.7911997574      1.42
- linear dependency detected:   32 /   33    min eigenvalue:    -3.3450e-15    max eigenvalue:     6.7280e-09
* Using canonical orthogonalization due to linear dependency

    32      0.0038080559   151.7911997574      1.46
- linear dependency detected:   33 /   34    min eigenvalue:    -3.8668e-15    max eigenvalue:     6.7281e-09
* Using canonical orthogonalization due to linear dependency

    33      0.0038080544   151.7911997573      1.45
- linear dependency detected:   34 /   35    min eigenvalue:    -7.9658e-15    max eigenvalue:     6.7281e-09
* Using canonical orthogonalization due to linear dependency

    34      0.0038080529   151.7911997573      1.46
- linear dependency detected:   35 /   36    min eigenvalue:    -6.5164e-15    max eigenvalue:     6.7281e-09
* Using canonical orthogonalization due to linear dependency

    35      0.0038080516   151.7911997573      1.46
- linear dependency detected:   36 /   37    min eigenvalue:    -5.4920e-15    max eigenvalue:     6.7281e-09
* Using canonical orthogonalization due to linear dependency

    36      0.0038080504   151.7911997573      1.45
- linear dependency detected:   37 /   38    min eigenvalue:    -7.4559e-15    max eigenvalue:     6.7282e-09
* Using canonical orthogonalization due to linear dependency

    37      0.0038080494   151.7911997573      1.46
- linear dependency detected:   38 /   39    min eigenvalue:    -8.6966e-15    max eigenvalue:     6.7282e-09
* Using canonical orthogonalization due to linear dependency

    38      0.0038080484   151.7911997573      1.43
- linear dependency detected:   39 /   40    min eigenvalue:    -6.3043e-15    max eigenvalue:     6.7282e-09
* Using canonical orthogonalization due to linear dependency

    39      0.0038080475   151.7911997573      1.42
- linear dependency detected:   40 /   41    min eigenvalue:    -1.0500e-14    max eigenvalue:     6.7282e-09
* Using canonical orthogonalization due to linear dependency

    40      0.0038080467   151.7911997573      1.44
- linear dependency detected:   41 /   42    min eigenvalue:    -5.6837e-15    max eigenvalue:     6.7282e-09
* Using canonical orthogonalization due to linear dependency

    41      0.0038080459   151.7911997573      1.47
- linear dependency detected:   42 /   43    min eigenvalue:    -6.0721e-15    max eigenvalue:     6.7282e-09
* Using canonical orthogonalization due to linear dependency

    42      0.0038080452   151.7911997573      1.48
- linear dependency detected:   43 /   44    min eigenvalue:    -1.0127e-14    max eigenvalue:     6.7282e-09
* Using canonical orthogonalization due to linear dependency

    43      0.0038080446   151.7911997573      1.48
- linear dependency detected:   44 /   45    min eigenvalue:    -1.0155e-14    max eigenvalue:     6.7282e-09
* Using canonical orthogonalization due to linear dependency

    44      0.0038080440   151.7911997573      1.64
- linear dependency detected:   45 /   46    min eigenvalue:    -8.2939e-15    max eigenvalue:     6.7282e-09
* Using canonical orthogonalization due to linear dependency

    45      0.0038080434   151.7911997573      1.55
- linear dependency detected:   46 /   47    min eigenvalue:    -6.5684e-15    max eigenvalue:     6.7282e-09
* Using canonical orthogonalization due to linear dependency

    46      0.0038080429   151.7911997573      1.54
- linear dependency detected:   47 /   48    min eigenvalue:    -8.6369e-15    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    47      0.0038080424   151.7911997572      1.48
- linear dependency detected:   48 /   49    min eigenvalue:    -9.7886e-15    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    48      0.0038080420   151.7911997572      1.45
- linear dependency detected:   49 /   50    min eigenvalue:    -1.2269e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    49      0.0038080416   151.7911997572      1.46
- linear dependency detected:   50 /   51    min eigenvalue:    -9.3614e-15    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    50      0.0038080412   151.7911997572      1.45
- linear dependency detected:   51 /   52    min eigenvalue:    -1.3487e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    51      0.0038080408   151.7911997572      1.54
- linear dependency detected:   52 /   53    min eigenvalue:    -1.1798e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    52      0.0038080405   151.7911997572      1.50
- linear dependency detected:   53 /   54    min eigenvalue:    -1.0188e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    53      0.0038080402   151.7911997572      1.51
- linear dependency detected:   54 /   55    min eigenvalue:    -9.5212e-15    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    54      0.0038080399   151.7911997572      1.49
- linear dependency detected:   55 /   56    min eigenvalue:    -8.1243e-15    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    55      0.0038080396   151.7911997572      1.48
- linear dependency detected:   56 /   57    min eigenvalue:    -1.2907e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    56      0.0038080393   151.7911997572      1.48
- linear dependency detected:   57 /   58    min eigenvalue:    -9.0228e-15    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    57      0.0038080391   151.7911997572      1.45
- linear dependency detected:   58 /   59    min eigenvalue:    -1.0106e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    58      0.0038080388   151.7911997572      1.48
- linear dependency detected:   59 /   60    min eigenvalue:    -1.1162e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    59      0.0038080386   151.7911997572      1.49
- linear dependency detected:   60 /   61    min eigenvalue:    -1.1221e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    60      0.0038080384   151.7911997572      1.46
- linear dependency detected:   61 /   62    min eigenvalue:    -1.0833e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    61      0.0038080382   151.7911997572      1.47
- linear dependency detected:   62 /   63    min eigenvalue:    -9.5992e-15    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    62      0.0038080380   151.7911997572      1.45
- linear dependency detected:   63 /   64    min eigenvalue:    -1.8595e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    63      0.0038080378   151.7911997572      1.46
- linear dependency detected:   64 /   65    min eigenvalue:    -1.2941e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    64      0.0038080377   151.7911997572      1.48
- linear dependency detected:   65 /   66    min eigenvalue:    -1.5033e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    65      0.0038080375   151.7911997572      1.50
- linear dependency detected:   66 /   67    min eigenvalue:    -1.5957e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    66      0.0038080374   151.7911997572      1.51
- linear dependency detected:   67 /   68    min eigenvalue:    -1.2695e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    67      0.0038080372   151.7911997572      1.47
- linear dependency detected:   68 /   69    min eigenvalue:    -1.6423e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    68      0.0038080371   151.7911997572      1.48
- linear dependency detected:   69 /   70    min eigenvalue:    -1.2264e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    69      0.0038080369   151.7911997572      1.47
- linear dependency detected:   70 /   71    min eigenvalue:    -1.7973e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    70      0.0038080368   151.7911997572      1.49
- linear dependency detected:   71 /   72    min eigenvalue:    -1.7339e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    71      0.0038080367   151.7911997572      1.50
- linear dependency detected:   72 /   73    min eigenvalue:    -1.3457e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    72      0.0038080366   151.7911997572      1.49
- linear dependency detected:   73 /   74    min eigenvalue:    -1.4050e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    73      0.0038080365   151.7911997572      1.51
- linear dependency detected:   74 /   75    min eigenvalue:    -1.7381e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    74      0.0038080364   151.7911997572      1.47
- linear dependency detected:   75 /   76    min eigenvalue:    -1.5687e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    75      0.0038080363   151.7911997572      1.47
- linear dependency detected:   76 /   77    min eigenvalue:    -1.3622e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    76      0.0038080362   151.7911997572      1.48
- linear dependency detected:   77 /   78    min eigenvalue:    -9.9842e-15    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    77      0.0038080361   151.7911997572      1.46
- linear dependency detected:   78 /   79    min eigenvalue:    -1.3477e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    78      0.0038080360   151.7911997572      1.48
- linear dependency detected:   79 /   80    min eigenvalue:    -1.2744e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    79      0.0038080359   151.7911997572      1.48
- linear dependency detected:   80 /   81    min eigenvalue:    -1.7111e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    80      0.0038080358   151.7911997572      1.48
- linear dependency detected:   81 /   82    min eigenvalue:    -1.6368e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    81      0.0038080358   151.7911997572      1.48
- linear dependency detected:   82 /   83    min eigenvalue:    -2.0525e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    82      0.0038080357   151.7911997572      1.50
- linear dependency detected:   83 /   84    min eigenvalue:    -1.6045e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    83      0.0038080356   151.7911997572      1.49
- linear dependency detected:   84 /   85    min eigenvalue:    -1.7029e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    84      0.0038080356   151.7911997572      1.52
- linear dependency detected:   85 /   86    min eigenvalue:    -1.2104e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    85      0.0038080355   151.7911997572      1.49
- linear dependency detected:   86 /   87    min eigenvalue:    -2.0542e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    86      0.0038080354   151.7911997572      1.46
- linear dependency detected:   87 /   88    min eigenvalue:    -2.0156e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    87      0.0038080354   151.7911997572      1.47
- linear dependency detected:   88 /   89    min eigenvalue:    -1.5512e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    88      0.0038080353   151.7911997572      1.46
- linear dependency detected:   89 /   90    min eigenvalue:    -1.5183e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    89      0.0038080352   151.7911997572      1.50
- linear dependency detected:   90 /   91    min eigenvalue:    -2.2305e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    90      0.0038080352   151.7911997572      1.50
- linear dependency detected:   91 /   92    min eigenvalue:    -1.8628e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    91      0.0038080351   151.7911997572      1.46
- linear dependency detected:   92 /   93    min eigenvalue:    -1.7681e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    92      0.0038080351   151.7911997572      1.49
- linear dependency detected:   93 /   94    min eigenvalue:    -2.5890e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    93      0.0038080350   151.7911997572      1.46
- linear dependency detected:   94 /   95    min eigenvalue:    -1.5689e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    94      0.0038080350   151.7911997572      1.46
- linear dependency detected:   95 /   96    min eigenvalue:    -2.3585e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    95      0.0038080350   151.7911997572      1.48
- linear dependency detected:   96 /   97    min eigenvalue:    -1.6829e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    96      0.0038080349   151.7911997572      1.45
- linear dependency detected:   97 /   98    min eigenvalue:    -1.7934e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    97      0.0038080349   151.7911997572      1.48
- linear dependency detected:   98 /   99    min eigenvalue:    -1.9011e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    98      0.0038080348   151.7911997572      1.46
- linear dependency detected:   99 /  100    min eigenvalue:    -2.1200e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

    99      0.0038080348   151.7911997572      1.49
- linear dependency detected:  100 /  101    min eigenvalue:    -2.3650e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

   100      0.0038080347   151.7911997572      1.49
- linear dependency detected:  101 /  102    min eigenvalue:    -1.7909e-14    max eigenvalue:     6.7283e-09
* Using canonical orthogonalization due to linear dependency

Then the program moves on to the next geometry and a bad gradient keeps getting calculated for the following steps.

I've found that this pattern is dependent on the "thresh_overlap" parameter. Sometimes these errors go away with a loose value such as 1e-4 but then they resurge at a later geometry.

Does anyone know what may be going on here?

Regards, Nuno

shiozaki commented 4 years ago

Please use XMS-CASPT2. MS-CASPT2 is an ill defined theory and that’s reflected in the instability of the Z vector equation. For theoretical backgrounds, read Granovsky 2011 JCP and perhaps some of mine.

On Thu, Jul 23, 2020 at 6:33 AM nagb notifications@github.com wrote:

I don't know if this has come up to any users before but I couldn't find anything while searching through the archive in here.

I am running an MS-CASPT2 optimisation and while the program is going through the gradient stage it gets stuck trying to solve the Z vector equations:

=== CASSCF Z-vector iteration ===

 0      0.0037950075   151.7911993374      1.64
  • linear dependency detected: 1 / 2 min eigenvalue: 9.6233e-09 max eigenvalue: 9.6233e-09

  • Using canonical orthogonalization due to linear dependency

    1 0.0038000891 151.7911995828 1.46

  • linear dependency detected: 2 / 3 min eigenvalue: -3.9371e-16 max eigenvalue: 7.1625e-09

  • Using canonical orthogonalization due to linear dependency

    2 0.0038091857 151.7911997637 1.67

  • linear dependency detected: 3 / 4 min eigenvalue: -2.6138e-16 max eigenvalue: 2.6369e-09

  • Using canonical orthogonalization due to linear dependency

    3 0.0038157240 151.7911997210 1.78

  • linear dependency detected: 4 / 5 min eigenvalue: -9.5739e-17 max eigenvalue: 5.2881e-09

  • Using canonical orthogonalization due to linear dependency

    4 0.0038124812 151.7911997586 1.62

  • linear dependency detected: 5 / 6 min eigenvalue: -5.8490e-16 max eigenvalue: 6.2254e-09

  • Using canonical orthogonalization due to linear dependency

    5 0.0038104955 151.7911997658 1.52

  • linear dependency detected: 6 / 7 min eigenvalue: -2.6349e-16 max eigenvalue: 6.5097e-09

  • Using canonical orthogonalization due to linear dependency

    6 0.0038095331 151.7911997648 1.49

  • linear dependency detected: 7 / 8 min eigenvalue: -3.1906e-16 max eigenvalue: 6.6177e-09

  • Using canonical orthogonalization due to linear dependency

    7 0.0038090163 151.7911997630 1.48

  • linear dependency detected: 8 / 9 min eigenvalue: -8.8894e-16 max eigenvalue: 6.6659e-09

  • Using canonical orthogonalization due to linear dependency

    8 0.0038087188 151.7911997616 1.50

  • linear dependency detected: 9 / 10 min eigenvalue: -2.4152e-15 max eigenvalue: 6.6901e-09

  • Using canonical orthogonalization due to linear dependency

    9 0.0038085355 151.7911997606 1.54

  • linear dependency detected: 10 / 11 min eigenvalue: -6.2078e-16 max eigenvalue: 6.7035e-09

  • Using canonical orthogonalization due to linear dependency

    10 0.0038084156 151.7911997598 1.50

  • linear dependency detected: 11 / 12 min eigenvalue: -1.0187e-15 max eigenvalue: 6.7114e-09

  • Using canonical orthogonalization due to linear dependency

    11 0.0038083332 151.7911997593 1.76

  • linear dependency detected: 12 / 13 min eigenvalue: -1.1373e-15 max eigenvalue: 6.7164e-09

  • Using canonical orthogonalization due to linear dependency

    12 0.0038082743 151.7911997589 1.77

  • linear dependency detected: 13 / 14 min eigenvalue: -5.9847e-16 max eigenvalue: 6.7196e-09

  • Using canonical orthogonalization due to linear dependency

    13 0.0038082308 151.7911997586 1.56

  • linear dependency detected: 14 / 15 min eigenvalue: -1.1299e-15 max eigenvalue: 6.7218e-09

  • Using canonical orthogonalization due to linear dependency

    14 0.0038081978 151.7911997584 1.53

  • linear dependency detected: 15 / 16 min eigenvalue: -2.1309e-15 max eigenvalue: 6.7233e-09

  • Using canonical orthogonalization due to linear dependency

    15 0.0038081722 151.7911997582 1.60

  • linear dependency detected: 16 / 17 min eigenvalue: -2.7386e-15 max eigenvalue: 6.7244e-09

  • Using canonical orthogonalization due to linear dependency

    16 0.0038081520 151.7911997581 1.88

  • linear dependency detected: 17 / 18 min eigenvalue: -1.6310e-15 max eigenvalue: 6.7252e-09

  • Using canonical orthogonalization due to linear dependency

    17 0.0038081357 151.7911997579 1.59

  • linear dependency detected: 18 / 19 min eigenvalue: -2.0190e-15 max eigenvalue: 6.7258e-09

  • Using canonical orthogonalization due to linear dependency

    18 0.0038081225 151.7911997578 1.73

  • linear dependency detected: 19 / 20 min eigenvalue: -2.1896e-15 max eigenvalue: 6.7263e-09

  • Using canonical orthogonalization due to linear dependency

    19 0.0038081116 151.7911997578 1.58

  • linear dependency detected: 20 / 21 min eigenvalue: -4.5704e-15 max eigenvalue: 6.7267e-09

  • Using canonical orthogonalization due to linear dependency

    20 0.0038081026 151.7911997577 1.44

  • linear dependency detected: 21 / 22 min eigenvalue: -4.2884e-15 max eigenvalue: 6.7269e-09

  • Using canonical orthogonalization due to linear dependency

    21 0.0038080949 151.7911997576 1.54

  • linear dependency detected: 22 / 23 min eigenvalue: -1.3493e-15 max eigenvalue: 6.7272e-09

  • Using canonical orthogonalization due to linear dependency

    22 0.0038080884 151.7911997576 1.50

  • linear dependency detected: 23 / 24 min eigenvalue: -1.4167e-15 max eigenvalue: 6.7273e-09

  • Using canonical orthogonalization due to linear dependency

    23 0.0038080829 151.7911997576 1.45

  • linear dependency detected: 24 / 25 min eigenvalue: -1.2044e-15 max eigenvalue: 6.7275e-09

  • Using canonical orthogonalization due to linear dependency

    24 0.0038080781 151.7911997575 1.44

  • linear dependency detected: 25 / 26 min eigenvalue: -1.4839e-15 max eigenvalue: 6.7276e-09

  • Using canonical orthogonalization due to linear dependency

    25 0.0038080740 151.7911997575 1.45

  • linear dependency detected: 26 / 27 min eigenvalue: -6.0602e-15 max eigenvalue: 6.7277e-09

  • Using canonical orthogonalization due to linear dependency

    26 0.0038080703 151.7911997575 1.52

  • linear dependency detected: 27 / 28 min eigenvalue: -1.2136e-15 max eigenvalue: 6.7278e-09

  • Using canonical orthogonalization due to linear dependency

    27 0.0038080672 151.7911997574 1.48

  • linear dependency detected: 28 / 29 min eigenvalue: -3.5270e-15 max eigenvalue: 6.7278e-09

  • Using canonical orthogonalization due to linear dependency

    28 0.0038080644 151.7911997574 1.53

  • linear dependency detected: 29 / 30 min eigenvalue: -1.6051e-15 max eigenvalue: 6.7279e-09

  • Using canonical orthogonalization due to linear dependency

    29 0.0038080619 151.7911997574 1.43

  • linear dependency detected: 30 / 31 min eigenvalue: -3.2801e-15 max eigenvalue: 6.7280e-09

  • Using canonical orthogonalization due to linear dependency

    30 0.0038080597 151.7911997574 1.51

  • linear dependency detected: 31 / 32 min eigenvalue: -1.3774e-15 max eigenvalue: 6.7280e-09

  • Using canonical orthogonalization due to linear dependency

    31 0.0038080577 151.7911997574 1.42

  • linear dependency detected: 32 / 33 min eigenvalue: -3.3450e-15 max eigenvalue: 6.7280e-09

  • Using canonical orthogonalization due to linear dependency

    32 0.0038080559 151.7911997574 1.46

  • linear dependency detected: 33 / 34 min eigenvalue: -3.8668e-15 max eigenvalue: 6.7281e-09

  • Using canonical orthogonalization due to linear dependency

    33 0.0038080544 151.7911997573 1.45

  • linear dependency detected: 34 / 35 min eigenvalue: -7.9658e-15 max eigenvalue: 6.7281e-09

  • Using canonical orthogonalization due to linear dependency

    34 0.0038080529 151.7911997573 1.46

  • linear dependency detected: 35 / 36 min eigenvalue: -6.5164e-15 max eigenvalue: 6.7281e-09

  • Using canonical orthogonalization due to linear dependency

    35 0.0038080516 151.7911997573 1.46

  • linear dependency detected: 36 / 37 min eigenvalue: -5.4920e-15 max eigenvalue: 6.7281e-09

  • Using canonical orthogonalization due to linear dependency

    36 0.0038080504 151.7911997573 1.45

  • linear dependency detected: 37 / 38 min eigenvalue: -7.4559e-15 max eigenvalue: 6.7282e-09

  • Using canonical orthogonalization due to linear dependency

    37 0.0038080494 151.7911997573 1.46

  • linear dependency detected: 38 / 39 min eigenvalue: -8.6966e-15 max eigenvalue: 6.7282e-09

  • Using canonical orthogonalization due to linear dependency

    38 0.0038080484 151.7911997573 1.43

  • linear dependency detected: 39 / 40 min eigenvalue: -6.3043e-15 max eigenvalue: 6.7282e-09

  • Using canonical orthogonalization due to linear dependency

    39 0.0038080475 151.7911997573 1.42

  • linear dependency detected: 40 / 41 min eigenvalue: -1.0500e-14 max eigenvalue: 6.7282e-09

  • Using canonical orthogonalization due to linear dependency

    40 0.0038080467 151.7911997573 1.44

  • linear dependency detected: 41 / 42 min eigenvalue: -5.6837e-15 max eigenvalue: 6.7282e-09

  • Using canonical orthogonalization due to linear dependency

    41 0.0038080459 151.7911997573 1.47

  • linear dependency detected: 42 / 43 min eigenvalue: -6.0721e-15 max eigenvalue: 6.7282e-09

  • Using canonical orthogonalization due to linear dependency

    42 0.0038080452 151.7911997573 1.48

  • linear dependency detected: 43 / 44 min eigenvalue: -1.0127e-14 max eigenvalue: 6.7282e-09

  • Using canonical orthogonalization due to linear dependency

    43 0.0038080446 151.7911997573 1.48

  • linear dependency detected: 44 / 45 min eigenvalue: -1.0155e-14 max eigenvalue: 6.7282e-09

  • Using canonical orthogonalization due to linear dependency

    44 0.0038080440 151.7911997573 1.64

  • linear dependency detected: 45 / 46 min eigenvalue: -8.2939e-15 max eigenvalue: 6.7282e-09

  • Using canonical orthogonalization due to linear dependency

    45 0.0038080434 151.7911997573 1.55

  • linear dependency detected: 46 / 47 min eigenvalue: -6.5684e-15 max eigenvalue: 6.7282e-09

  • Using canonical orthogonalization due to linear dependency

    46 0.0038080429 151.7911997573 1.54

  • linear dependency detected: 47 / 48 min eigenvalue: -8.6369e-15 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    47 0.0038080424 151.7911997572 1.48

  • linear dependency detected: 48 / 49 min eigenvalue: -9.7886e-15 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    48 0.0038080420 151.7911997572 1.45

  • linear dependency detected: 49 / 50 min eigenvalue: -1.2269e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    49 0.0038080416 151.7911997572 1.46

  • linear dependency detected: 50 / 51 min eigenvalue: -9.3614e-15 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    50 0.0038080412 151.7911997572 1.45

  • linear dependency detected: 51 / 52 min eigenvalue: -1.3487e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    51 0.0038080408 151.7911997572 1.54

  • linear dependency detected: 52 / 53 min eigenvalue: -1.1798e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    52 0.0038080405 151.7911997572 1.50

  • linear dependency detected: 53 / 54 min eigenvalue: -1.0188e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    53 0.0038080402 151.7911997572 1.51

  • linear dependency detected: 54 / 55 min eigenvalue: -9.5212e-15 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    54 0.0038080399 151.7911997572 1.49

  • linear dependency detected: 55 / 56 min eigenvalue: -8.1243e-15 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    55 0.0038080396 151.7911997572 1.48

  • linear dependency detected: 56 / 57 min eigenvalue: -1.2907e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    56 0.0038080393 151.7911997572 1.48

  • linear dependency detected: 57 / 58 min eigenvalue: -9.0228e-15 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    57 0.0038080391 151.7911997572 1.45

  • linear dependency detected: 58 / 59 min eigenvalue: -1.0106e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    58 0.0038080388 151.7911997572 1.48

  • linear dependency detected: 59 / 60 min eigenvalue: -1.1162e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    59 0.0038080386 151.7911997572 1.49

  • linear dependency detected: 60 / 61 min eigenvalue: -1.1221e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    60 0.0038080384 151.7911997572 1.46

  • linear dependency detected: 61 / 62 min eigenvalue: -1.0833e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    61 0.0038080382 151.7911997572 1.47

  • linear dependency detected: 62 / 63 min eigenvalue: -9.5992e-15 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    62 0.0038080380 151.7911997572 1.45

  • linear dependency detected: 63 / 64 min eigenvalue: -1.8595e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    63 0.0038080378 151.7911997572 1.46

  • linear dependency detected: 64 / 65 min eigenvalue: -1.2941e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    64 0.0038080377 151.7911997572 1.48

  • linear dependency detected: 65 / 66 min eigenvalue: -1.5033e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    65 0.0038080375 151.7911997572 1.50

  • linear dependency detected: 66 / 67 min eigenvalue: -1.5957e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    66 0.0038080374 151.7911997572 1.51

  • linear dependency detected: 67 / 68 min eigenvalue: -1.2695e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    67 0.0038080372 151.7911997572 1.47

  • linear dependency detected: 68 / 69 min eigenvalue: -1.6423e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    68 0.0038080371 151.7911997572 1.48

  • linear dependency detected: 69 / 70 min eigenvalue: -1.2264e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    69 0.0038080369 151.7911997572 1.47

  • linear dependency detected: 70 / 71 min eigenvalue: -1.7973e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    70 0.0038080368 151.7911997572 1.49

  • linear dependency detected: 71 / 72 min eigenvalue: -1.7339e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    71 0.0038080367 151.7911997572 1.50

  • linear dependency detected: 72 / 73 min eigenvalue: -1.3457e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    72 0.0038080366 151.7911997572 1.49

  • linear dependency detected: 73 / 74 min eigenvalue: -1.4050e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    73 0.0038080365 151.7911997572 1.51

  • linear dependency detected: 74 / 75 min eigenvalue: -1.7381e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    74 0.0038080364 151.7911997572 1.47

  • linear dependency detected: 75 / 76 min eigenvalue: -1.5687e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    75 0.0038080363 151.7911997572 1.47

  • linear dependency detected: 76 / 77 min eigenvalue: -1.3622e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    76 0.0038080362 151.7911997572 1.48

  • linear dependency detected: 77 / 78 min eigenvalue: -9.9842e-15 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    77 0.0038080361 151.7911997572 1.46

  • linear dependency detected: 78 / 79 min eigenvalue: -1.3477e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    78 0.0038080360 151.7911997572 1.48

  • linear dependency detected: 79 / 80 min eigenvalue: -1.2744e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    79 0.0038080359 151.7911997572 1.48

  • linear dependency detected: 80 / 81 min eigenvalue: -1.7111e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    80 0.0038080358 151.7911997572 1.48

  • linear dependency detected: 81 / 82 min eigenvalue: -1.6368e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    81 0.0038080358 151.7911997572 1.48

  • linear dependency detected: 82 / 83 min eigenvalue: -2.0525e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    82 0.0038080357 151.7911997572 1.50

  • linear dependency detected: 83 / 84 min eigenvalue: -1.6045e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    83 0.0038080356 151.7911997572 1.49

  • linear dependency detected: 84 / 85 min eigenvalue: -1.7029e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    84 0.0038080356 151.7911997572 1.52

  • linear dependency detected: 85 / 86 min eigenvalue: -1.2104e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    85 0.0038080355 151.7911997572 1.49

  • linear dependency detected: 86 / 87 min eigenvalue: -2.0542e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    86 0.0038080354 151.7911997572 1.46

  • linear dependency detected: 87 / 88 min eigenvalue: -2.0156e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    87 0.0038080354 151.7911997572 1.47

  • linear dependency detected: 88 / 89 min eigenvalue: -1.5512e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    88 0.0038080353 151.7911997572 1.46

  • linear dependency detected: 89 / 90 min eigenvalue: -1.5183e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    89 0.0038080352 151.7911997572 1.50

  • linear dependency detected: 90 / 91 min eigenvalue: -2.2305e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    90 0.0038080352 151.7911997572 1.50

  • linear dependency detected: 91 / 92 min eigenvalue: -1.8628e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    91 0.0038080351 151.7911997572 1.46

  • linear dependency detected: 92 / 93 min eigenvalue: -1.7681e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    92 0.0038080351 151.7911997572 1.49

  • linear dependency detected: 93 / 94 min eigenvalue: -2.5890e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    93 0.0038080350 151.7911997572 1.46

  • linear dependency detected: 94 / 95 min eigenvalue: -1.5689e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    94 0.0038080350 151.7911997572 1.46

  • linear dependency detected: 95 / 96 min eigenvalue: -2.3585e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    95 0.0038080350 151.7911997572 1.48

  • linear dependency detected: 96 / 97 min eigenvalue: -1.6829e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    96 0.0038080349 151.7911997572 1.45

  • linear dependency detected: 97 / 98 min eigenvalue: -1.7934e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    97 0.0038080349 151.7911997572 1.48

  • linear dependency detected: 98 / 99 min eigenvalue: -1.9011e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    98 0.0038080348 151.7911997572 1.46

  • linear dependency detected: 99 / 100 min eigenvalue: -2.1200e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    99 0.0038080348 151.7911997572 1.49

  • linear dependency detected: 100 / 101 min eigenvalue: -2.3650e-14 max eigenvalue: 6.7283e-09

  • Using canonical orthogonalization due to linear dependency

    100 0.0038080347 151.7911997572 1.49

  • linear dependency detected: 101 / 102 min eigenvalue: -1.7909e-14 max eigenvalue: 6.7283e-09
  • Using canonical orthogonalization due to linear dependency

Then the program moves on to the next geometry and a bad gradient keeps getting calculated for the following steps.

I've found that this pattern is dependent on the "thresh_overlap" parameter. Sometimes these errors go away with a loose value such as 1e-4 but then they resurge at a later geometry.

Does anyone know what may be going on here?

Regards, Nuno

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nagb commented 4 years ago

Thanks for commenting.

I will try the XMS variant but I was under the impression that XMS-CASPT2 is not so good for excited state energies (Lindh et al https://dx.doi.org/10.1021/acs.jctc.9b01129) hence my hesitation.

Full disclosure I am also using a non-standard imaginary shift of 0.5 au since from a OpenMOLCAS single point run I see some intruder states. In BAGEL I don't know how to spot them.

shiozaki commented 4 years ago

The usefulness of XMS-CASPT2 has been established so I don't intend to argue here (for that matter, I don't agree with Roland, except when you are studying very high lying state (like 30th excited state)). In any event, the deficiency of MS-CASPT2 Z vector cannot be fixed because the problem lies in the MS-CASPT2 parameterization.

On a separate note, likely, there are multiple sources of intruders. MOLCAS has more sources of intruders than BAGEL does; so it may be that an imaginary shift of 0.5 is not necessary. But you never know. Just calculate something with different shifts and see how it behaves. The same amount of information as Molcas is printed out in BAGEL.

Since I am not in academia any longer, I have no time to help you with specific input files, but hope this helps. I will close the issue.

PS: When XMS-CAPST2 vs MS-CASPT2 accuracy is the issue, it means that CASPT2 ansaz itself is not sufficient, so you'd better do something other than CASPT2.

PPS: I think the cause of slow adaptation of XMS-CASPT2 is because it was proposed by Granovsky in Russia who didn't travel to the western world (he passed away last year), and because Molcas is not setup to implement XMS-CASPT2 correctly (they use a state-specific Fock operator instead of state averaged one.

nagb commented 4 years ago

Thank you very much for those insightful comments! I will take these into consideration when I run more trials.

nagb commented 4 years ago

Just as a follow-up, I can confirm that the Z-vector equations with XMS-CASPT2 are numerically stable for my system and the optimisation goes smoothly.

shiozaki commented 4 years ago

Cool, thanks for letting me know.