# [molpro-user] Ta atom electronic structure

Hyungjun Kim hyungjun96 at kaist.ac.kr
Thu Feb 12 02:33:59 GMT 2015

```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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