Basis set generation help

Das scpem... at lbl.gov
Wed Jul 11 05:50:41 UTC 2012


P.S: Changing the starting guess for the exponents does not fix the problem 
as the program sooner or later gives the same linear dependency error. I 
have tried several different starting guesses where the exponents are 
substantially different. This problem does not occur for lighter elements.

On Tuesday, July 10, 2012 10:40:34 PM UTC-7, Das wrote:
>
> Hi all,
>   I am trying to generate optimized basis sets for Lanthanide and Actinide 
> elements using the gaussian basis generation program *optbas*. I tried to 
> optimize a basis set for Nd using the *basis-Nd-q14-g6* file that is 
> provided in the *${CP2K_HOME}/trunk/basis_sets/inpout/PADE/* directory as 
> a starting point. However, the program crashes with the error
> *"diag: Overlap matrix has linear dependency"*
> *
> *
> How do I avoid this error?
> I am pasting the input and output below
>
> *========input===================================*
> *
> &ATOM
>   NAME  Nd
>   PPOT
>   ZVAL  60
>   ZEFF  14
>   LMAX  3
>   OCCU
>            2        2 2
>          1          6
>          1          0
>          1          4
>   MIXI  0.2
>   CONV  1.0D-12
>   ITER  200
>   IPPN  100
>   XCFN  PADE
>   OPTI  1.0D-8
> &END
>
> &BASIS
>   GAUS
>   6 
>       2.365739530243      2.352254571258      0.766552037600     
>  0.333931373408      0.115924677467      0.031752598879 
>  1 2 3 4 5 6
> 6 
>       2.365739530243      2.352254571258      0.766552037600     
>  0.333931373408      0.115924677467      0.031752598879 
>  1 2 3 4 5 6
> 6 
>       2.365739530243      2.352254571258      0.766552037600     
>  0.333931373408      0.115924677467      0.031752598879 
>  1 2 3 4 5 6
> 6 
>       2.365739530243      2.352254571258      0.766552037600     
>  0.333931373408      0.115924677467      0.031752598879 
>  1 2 3 4 5 6
> 6 
>       2.365739530243      2.352254571258      0.766552037600     
>  0.333931373408      0.115924677467      0.031752598879 
>  1 2 3 4 5 6
>
> &END
>  &POTENTIAL
>      GOEDECKER
>  4                                    LMAX
>        .529166698                                 RC
>    2    17.815030430     -.594797667   #C  C1 C2
>        .502999856  2   1.529109884    .834136795  -2.153731944 H(s) 11 12 
> 22           
>        .467012905  2    .721553461    .696195481  -1.647499204 H(p) 11 12 
> 22           
>        .325289583  1   -.543240170 H(d) 11                 
>        .294742814  1 -18.520227599 H(f) 11                 
>  &END
> *
> *===============================================*
> *
> *
> *===============output===========================*
> *
>   
>         PROGRAM ATOM
>         ------------
>  reading input file...
>   LMAX =           3
>   OCCU(           1 ,           0 ) =    2.00000000000000     
>   OCCU(           2 ,           0 ) =    2.00000000000000     
>   OCCU(           1 ,           1 ) =    6.00000000000000     
>   OCCU(           1 ,           2 ) =   0.000000000000000E+000
>   OCCU(           1 ,           3 ) =    4.00000000000000     
>   NALPHA(           0 ) =            6
>   GAUS(           1 ,           0 ) =    2.36573953024300     
>   GAUS(           2 ,           0 ) =    2.35225457125800     
>   GAUS(           3 ,           0 ) =   0.766552037600000     
>   GAUS(           4 ,           0 ) =   0.333931373408000     
>   GAUS(           5 ,           0 ) =   0.115924677467000     
>   GAUS(           6 ,           0 ) =   3.175259887900000E-002
>   ALPP(           1 ,           0 ) =            1
>   ALPP(           2 ,           0 ) =            2
>   ALPP(           3 ,           0 ) =            3
>   ALPP(           4 ,           0 ) =            4
>   ALPP(           5 ,           0 ) =            5
>   ALPP(           6 ,           0 ) =            6
>   NALPHA(           1 ) =            6
>   GAUS(           1 ,           1 ) =    2.36573953024300     
>   GAUS(           2 ,           1 ) =    2.35225457125800     
>   GAUS(           3 ,           1 ) =   0.766552037600000     
>   GAUS(           4 ,           1 ) =   0.333931373408000     
>   GAUS(           5 ,           1 ) =   0.115924677467000     
>   GAUS(           6 ,           1 ) =   3.175259887900000E-002
>   ALPP(           1 ,           1 ) =            1
>   ALPP(           2 ,           1 ) =            2
>   ALPP(           3 ,           1 ) =            3
>   ALPP(           4 ,           1 ) =            4
>   ALPP(           5 ,           1 ) =            5
>   ALPP(           6 ,           1 ) =            6
>   NALPHA(           2 ) =            6
>   GAUS(           1 ,           2 ) =    2.36573953024300     
>   GAUS(           2 ,           2 ) =    2.35225457125800     
>   GAUS(           3 ,           2 ) =   0.766552037600000     
>   GAUS(           4 ,           2 ) =   0.333931373408000     
>   GAUS(           5 ,           2 ) =   0.115924677467000     
>   GAUS(           6 ,           2 ) =   3.175259887900000E-002
>   ALPP(           1 ,           2 ) =            1
>   ALPP(           2 ,           2 ) =            2
>   ALPP(           3 ,           2 ) =            3
>   ALPP(           4 ,           2 ) =            4
>   ALPP(           5 ,           2 ) =            5
>   ALPP(           6 ,           2 ) =            6
>   NALPHA(           3 ) =            6
>   GAUS(           1 ,           3 ) =    2.36573953024300     
>   GAUS(           2 ,           3 ) =    2.35225457125800     
>   GAUS(           3 ,           3 ) =   0.766552037600000     
>   GAUS(           4 ,           3 ) =   0.333931373408000     
>   GAUS(           5 ,           3 ) =   0.115924677467000     
>   GAUS(           6 ,           3 ) =   3.175259887900000E-002
>   ALPP(           1 ,           3 ) =            1
>   ALPP(           2 ,           3 ) =            2
>   ALPP(           3 ,           3 ) =            3
>   ALPP(           4 ,           3 ) =            4
>   ALPP(           5 ,           3 ) =            5
>   ALPP(           6 ,           3 ) =            6
>   Unknown keyword :6         
>   Unknown keyword :2.36      
>   Unknown keyword :2.35      
>   Unknown keyword :0.76      
>   Unknown keyword :0.33      
>   Unknown keyword :0.11      
>   Unknown keyword :0.03      
>   Unknown keyword :1         
>   Unknown keyword :2         
>   Unknown keyword :3         
>   Unknown keyword :4         
>   Unknown keyword :5         
>   Unknown keyword :6         
>   Unknown keyword :          
>  Zval =    60.0000000000000     
>  finished reading input file.
>   
>   
>  Basis Optimization for atom ND
>   
>  Pseudopotential calculation with  14.00 valence electrons.
>  Goedecker pseudopotential
>  Effective core charge is  14.0 .
>   
>  The exchange correlation functional is LDA .
>   
>   
>    100 points
>
> r(1) =       0.000000007128
> r(n) =      27.592628200894
>      1        14.00000000000004  -3.553E-14       -45.65611536880110
>      2        14.00000000004239  -4.239E-11       -49.85166017152175
>      3        13.99999999999986   1.439E-13       -52.55235239913090
>      4        14.00000000004143  -4.143E-11       -52.33646383858017
>      5        14.00000000001213  -1.213E-11       -52.68168868070856
>      6        14.00000000001491  -1.491E-11       -52.67944455717392
>      7        14.00000000001312  -1.312E-11       -52.68180921276654
>      8        14.00000000001172  -1.172E-11       -52.68233730628295
>      9        14.00000000001173  -1.173E-11       -52.68233759472056
>     10        14.00000000001277  -1.277E-11       -52.68233759651003
>     11        14.00000000001319  -1.319E-11       -52.68233759651931
>     12        14.00000000001227  -1.227E-11       -52.68233759651482
>     13        14.00000000001192  -1.192E-11       -52.68233759653047
>     14        14.00000000001172  -1.172E-11       -52.68233759651416
>     15        14.00000000001300  -1.300E-11       -52.68233759652121
>     16        14.00000000001242  -1.242E-11       -52.68233759650462
>     17        14.00000000001131  -1.131E-11       -52.68233759652614
>     18        14.00000000001181  -1.181E-11       -52.68233759652527
>    scf-loop:           18  steps        E=  -52.6823375965253     
>  initializing Hessian as diagonal matrix...
>            1 New direction:
>      800111111
>    100 points
>
> r(1) =       0.000000007128
> r(n) =      27.592628200894
>      1        13.95227039006375   4.773E-02       -52.58518483142689
>  ndep =           1
>  Overlap matrix S
>     1.000000    0.999994    0.797329    0.534326    0.274189    0.109328
>     0.999994    1.000000    0.799048    0.536027    0.275242    0.109778
>     0.797329    0.799048    1.000000    0.881699    0.555306    0.244363
>     0.534326    0.536027    0.881699    1.000000    0.818107    0.422632
>     0.274189    0.275242    0.555306    0.818107    1.000000    0.744800
>     0.109328    0.109778    0.244363    0.422632    0.744800    1.000000
>  Eigenvalues and eigenvectors of the overlap matrix S
>     0.000001    0.705019    0.101786    0.193138    0.326513   -0.413550   
>  0.421486
>     0.015285   -0.709131    0.089705    0.188077    0.324076   -0.412999   
>  0.422042
>     0.118939    0.007650   -0.582711   -0.563991   -0.301587   -0.141783   
>  0.480880
>     0.511976   -0.004433    0.689136   -0.083849   -0.525255    0.176392   
>  0.459386
>     1.551712    0.001519   -0.390025    0.659794   -0.117125    0.506588   
>  0.377094
>     3.802087   -0.000358    0.122530   -0.408508    0.638591    0.592081   
>  0.244436
>  alpha:  
>         2.3656493935        2.3523546985        0.7665441701       
>  0.3339315383
>         0.1159253367        0.0317525342
>         2.3656493935        2.3523546985        0.7665441701       
>  0.3339315383
>         0.1159253367        0.0317525342
>         2.3656493935        2.3523546985        0.7665441701       
>  0.3339315383
>         0.1159253367        0.0317525342
>         2.3656493935        2.3523546985        0.7665441701       
>  0.3339315383
>         0.1159253367        0.0317525342
>  galpha:  
>         0.0018321464        0.0018715621        0.0175072478       
> -0.0208608560
>        -0.0272090252       -0.0215773321
>        -0.0018546657       -0.0019278218       -0.0132979508       
> -0.0058427766
>         0.0007191953       -0.0000378422
>         0.0000000000        0.0000000000        0.0000000000       
>  0.0000000000
>         0.0000000000        0.0000000000
>         0.0000386246        0.0000381637       -0.0041959078       
>  0.0267021539
>         0.0264407750        0.0216793080
> diag: Overlap matrix has linear dependency
> *
> *===============================================*
> *
> *
> It seems that the program makes two of the exponents very similar causing 
> off-diagonal elements in the overlap matrix to be very close to 1.
> I see this behaviour for pretty much all of the Lanthanide elements I have 
> looked at. In all cases, I've used the example basis files provided 
> in ${CP2K_HOME}/trunk/basis_sets/inpout/PADE/ as inputs to optbas after 
> merely adding the *OPTI 1.0D-8* flag so that optbas perfoms an 
> optimization.
>
> Are there any options one can pass to optbas to prevent this linear 
> dependency during the optimization?
>
> Any help is much appreciated.
>
> Many Thanks,
> -Das
>
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