[molpro-user] Ta atom electronic structure

[Hyungjun Kim]

Dear Molpro Users,


I have been calculating the electronic structure of Ta atom using CASSCF with aug-cc-pVTZ-PP basis sets.


The ground state of Ta atom is known to be 5d3 6s2. (The corresponding term symbol is ^4F)


I would like to obtain all microstates energy which can be generated from 5d3 6s2, such as ^4P, ^2H, ^2G, ^2F, ^2D(two), ^2P.


Actually I can successfully simulate the 4F and 4P states using following input.


*******************************
{multi;
   occ,4,1,1,1,1,1,1,0;
closed,1,1,1,0,1,0,0,0;
config;
    wf,13,1,3;state,1;
    select
    con,2 0 0 1 1 1
   wf,13,4,3;state,3;
    select
    con,2 1 0 0 1 1
    con,2 0 1 0 1 1
    con,2 1 1 1 0 0
   wf,13,6,3;state,3;
    select
    con,2 1 0 1 0 1
    con,2 0 1 1 0 1
    con,2 1 1 0 1 0
   wf,13,7,3;state,3;
    select
    con,2 1 0 1 1 0
    con,2 0 1 1 1 0
    con,2 1 1 0 0 1
}
*******************************


D2h symmetry is employed and the corresponding MULTI orbitals are [6s, 5d, 5d](in Irrep1), [5d](in Irrep4), [5d](in Irrep6), and [5d](in Irrep7).


In the quartet case, the number of CSF and the number of state are equal and there is no problem.


The problem occurs for the doublet term symbol.(^2H, ^2G, ^2F, ^2D(two), ^2P.)


The number of following selected configurations is only 30 (in my input file below, 9+7+7+7=30), but the sum of the microstates of the above doublet term symbols are 40.(11+9+7+5*2+3=40)


If the number of state is increased upto 10 which is larger than the number of CSF(9 for Irrep1, 7 for Irrep 4,6,7), MOLPRO yields the error message.


This is my input file for the doublet term symbols. 


*******************************
memory,1000,m;


geometry={Ta}


basis=aug-cc-pVTZ-PP


{rhf,maxit=100
   occ,4,1,1,1,1,0,0,0
closed,2,1,1,0,1,0,0,0
    wf,13,4,3;
OrbPrint,3
}


{multi;
   occ,4,1,1,1,1,1,1,0;
closed,1,1,1,0,1,0,0,0;
config;
    wf,13,1,1;state,9;
    select
     con,2 2 1 0 0 0
     con,2 1 2 0 0 0
     con,2 1 0 2 0 0
     con,2 1 0 0 2 0
     con,2 1 0 0 0 2
     con,2 0 1 2 0 0
     con,2 0 1 0 2 0
     con,2 0 1 0 0 2
     con,2 0 0 1 1 1
   wf,13,4,1;state,7;
    select
     con,2 2 0 1 0 0
     con,2 0 2 1 0 0
     con,2 0 0 1 2 0
     con,2 0 0 1 0 2
     con,2 1 1 1 0 0
     con,2 1 0 0 1 1
     con,2 0 1 0 1 1
   wf,13,6,1;state,7;
    select
     con,2 2 0 0 1 0
     con,2 0 2 0 1 0
     con,2 0 0 2 1 0
     con,2 0 0 0 1 2
     con,2 1 1 0 1 0
     con,2 1 0 1 0 1
     con,2 0 1 1 0 1
   wf,13,7,1;state,7;
    select
     con,2 2 0 0 0 1
     con,2 0 2 0 0 1
     con,2 0 0 0 2 1
     con,2 0 0 2 0 1
     con,2 1 1 0 0 1
     con,2 1 0 1 1 0
     con,2 0 1 1 1 0
}
*******************************


I don't know how to include all the microstates of the doublet term symbol? 
Could you give me any advice?


Best regards,


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