[molpro-user] Un

[Alexander Mitrushchenkov]

Lukasz,

It might be indeed that such a light atom is not implemented for ECP density 
guess; you can always try to use a simple H0 diagonalization as a start, 
something like

start,h0

inside RHF block. 

With CI it might be tricky but normally it means that your reference state
is not good. Usually increasing nstati by 1 or 2 helps but if not this means 
that reference is really bad and then your CI would have been meaningless 
anyway. Then the orbital investigation/plot could give a hint.

Cheers,

Sasha

On Wednesday, December 08, 2010 02:04:04 pm Łukasz Miądowicz wrote:
> Dear Molpro Users!
> 
> I'm trying to do some calculations of Spin - Orbit coupling for KLi
> diatomic molecule
> I'm using ECP approach in my calculations rather than Breit-Pauli operator.
> 
> Here's my input file:
> 
> ***,kli
> 
> memory,100,m;
> 
> GPRINT,BASIS,DISTANCE,ANGLES,ORBITAL,CIVECTOR,PAIRS,CP,CS,REF,PSPACE,MICRO,
> VARIABLE,OPTIONS,THRESHOL,ZMATRIX,MPPERR,OPERATOR,EXTENSIO; rvec=[30.]
> !rvec=[70,40.,20.,10.,3.]
> 
> do i=1,#rvec
> rkli=rvec(i)
> 
> geometry={li;k,li,rkli}
> 
> basis={
> 
> ecp,li,ecp2sdf;
> 
> ECP,k,18,3,3;
> 1; 2,1.000000,0.000000;
> 1; 2,0.853000,13.564000;
> 1; 2,0.369600,2.648000;
> 1; 2,0.663900,-4.517000;
> 
> 1; 2,0.853000,-0.4;
> 1; 2,0.369600,1.0;
> 1; 2,0.663900,1.0;
> 
> 
> s,li,ecp2sdf;
> s,li,15.385230,0.010159;
> 
> p,li,ecp2sdf;
> p,li,4.076012,0.007058;
> 
> d,li,cc-pV5Z;
> d,li,1.043103,0.026579;
> 
> f,li,cc-pV5Z;
> f,li,0.556818,0.055000;
> 
> s,k,ecp18sdf;c;
> s,k,4.535573,0.009433;
> 
> p,k,ecp18sdf;c;
> p,k,0.940156,0.004358;
> 
> d,k,ecp10mdf;c;
> d,k,3.954897,0.010789;
> 
> f,k,ecp10mdf;c;
> f,k,1.680236,0.029604;
> 
> }
> 
> {cpp,init,1;
> li,1,0.1915,,,0.831;}
> 
> {cpp,init,1;
> k,1,5.354,,,0.29;}
> 
> 
> {rhf;occ,1,0,0,0;wf,2,1,0;}
> 
> 
> {multi,maxit=50;occ,3,2,2,0;
> wf,2,1,2;state,3;
> wf,2,2,2;state,2;
> wf,2,3,2;state,2;}
> 
> 
> {ci,nocheck;occ,3,2,2;option,maxit=199,maxiti=500;wf,2,1,0;save,
> 3010.1;state,3;}
> {ci,nocheck;occ,3,2,2;option,maxit=199,maxiti=500;wf,2,1,2;save,
> 3012.1;state,3;}
> 
> lsint;
> 
> {ci;hlsmat,ecp,3010.1,3012.1;}
> 
> 
> 
> I get some errors:
> 
> 1) First is (this error occures even if I do simple RHF procedure for
> molecules that contains Li )
> When I was making my calculations in 2006.1 version of molpro (without SO
> coupling, just simple rhf, multi and ci) I didn't get this error.
> Why Li is treated as a unimplemented atom ?
> 
> 1PROGRAM * RHF-SCF (CLOSED SHELL)       Authors: W. Meyer, H.-J. Werner
> 
> 
>  NUMBER OF ELECTRONS:       1+    1-    SPACE SYMMETRY=1    SPIN
> SYMMETRY=Singlet
>  CONVERGENCE THRESHOLDS:    1.00E-05 (Density)    1.00E-07 (Energy)
>  MAX. NUMBER OF ITERATIONS:       60
>  INTERPOLATION TYPE:            DIIS
>  INTERPOLATION STEPS:              2 (START)      1 (STEP)
>  LEVEL SHIFTS:                  0.00 (CLOSED)  0.00 (OPEN)
> 
>  Number of closed-shell orbitals:    1 (   1   0   0   0 )
> 
> 
> 
>  Unimplemented atom: LI       No density guess!
> 
> 
> 2) Second is in CI procedure :
> 
> Coefficients of doubly external configurations greater than 0.0500000
>  =====================================================================
> 
>  PAIR    I     J   ->   K     L     NP  SYM  REF     COEFFICIENTS
> 
>    1    2.3   2.3      4.2   4.2     1   1    3    0.00000354 -0.00024202
> -0.15885604
>    1    2.3   2.3      4.3   4.3     1   1    3    0.00000354 -0.00024205
> -0.15884053
>    1    2.3   2.3      4.2  10.2     1   1    3    0.00000583  0.00006029
>  0.09289244
>    1    2.3   2.3      4.3  10.3     1   1    3    0.00000583  0.00006029
>  0.09289243
>    1    2.3   2.3     10.2  10.2     1   1    3   -0.00000410  0.00006513
> -0.05687544
>    1    2.3   2.3     10.3  10.3     1   1    3   -0.00000410  0.00006514
> -0.05687519
> 
>  ? Error
>  ? Insufficient overlap
>  ? The problem occurs in cihdia
> 
> 
> I tried to increase NSTATI but without any results, if I increase NSTATI
> too much i get
> "MORE STATES THAN CONFIGURATIONS SPECIFIED"
> 
> 
> Can you have any ideas ?
> 
> Do you have any practice in calculating SO Coupling but with using ECP
> approach rather than Breit-Pauli operator?
> 
> 
> Thank you very much,
> 
> Łukasz Miądowicz

-- 
Dr. Alexander Mitrushchenkov, IGR
Laboratoire de Modélisation et Simulation Multi Echelle
UMR 8208 CNRS
Université Paris-Est Marne-la-Vallée
5 Bd Descartes
77454 Marne la Vallée, Cedex 2, France

Phone:    +33(0)160957316
Fax:      +33(0)160957320
e-mail:   Alexander.Mitrushchenkov at univ-mlv.fr
-----------------------------------------