[molpro-user] LS Integral format via MATROP
Alexander Mitrushchenkov
Alexander.Mitrushchenkov at u-pem.fr
Fri Jun 17 14:53:06 CEST 2016
Dear Paul,
When molpro calculates spin-orbit matrix elements, via tranls or hlsmat
directives, it uses the full BP hamiltonian as described in the cited
paper. The only exception is the external part of MRCI wavefunction
where effective Fock matrix technique is used, as also described in the
paper. The one-electron part (denoted g) is available as in your input,
and indeed it is not scaled by relativistic factor 1/c**2 (and of cause
it does not contain spin). The two electron part is stored internally
and is not available to the user. So, unless you have special purpose,
the use of 'lsz' one-electron operator via matrop has no obvious use.
Best wishes,
Alexander
Le 16/06/2016 13:34, Murphy, Paul a écrit :
> Hello,
>
> I am running jobs which access the LS property integrals in Molpro using the following example for the Boron atom with the single unpaired electron in a p orbital. The corresponding prop_ints_lsz integral file is attached at the bottom.
>
> My question is - can anyone advise me on the format of these LSZ integrals including the Spin Orbit Hamiltonian used in their formation?
>
> From the "Spin Orbit Matrix Elements for MRCI" paper by Berning et al., Mol. Phys., 2000, 98, 21, 1823-1833 I can see the Breit-Pauli Hamiltonian in equation (1).
> Equation (2) contains the one electron part only. Is this equation (2) the correct Hamiltonian for these integrals I am looking at?
> Do the integrals contain the Z_K term? What about the 1/c^2 term? Is that included?
> My feeling is that the Z_K term is included in the integrals below but the 1/c^2 term is not. Also I suspect these integrals are only one electron terms and have no approximation to the two electron terms. Finally I am quite sure the s term is not included either.
>
> If anyone can clarify this for me I would be very grateful.
>
> Rgds
> Paul Murphy
>
> ***,SOC calculation for the B-atom
> memory,1000,m
>
> geometry={b}
> basis={spd,b,vdz}
>
> !rhf for doublet pz state
> {rhf;occ,2,,,,1;wf,5,5,1}
>
> lsint ! determine so integrals
>
> !Finally print the spin orbit integrals from the canonical orbitals
> {matrop;
> load, hforbs_lsz, orb, 2100.2, canonical !load the hf canonical orbs
> load, lsz_op, oper, lsz; !load the spin orbit operator
> print, lsz_op
> tran, lsz_ints, lsz_op, hforbs_lsz; !transform HF orbitals with LSZ operator
> print, lsz_ints
> write, lsz_ints, prop_ints_lsz, new
> }
>
>
>
> BEGIN_DATA,
> # MATRIX LSZ_INTS OPER SYMMETRY=4
> 0.00000000,
> 0.00000000,
> 0.00000000,
> 0.00000000,
> 1.70966084,
> 0.00000000,
> 0.00000000,
> -0.00000000,
> 0.00000000,
> -0.00000000,
> 0.00000000,
> 2.03282321, -2.77364997, 5.10059901, 11.01881990,
> -2.77364997, 4.19157832, -7.97251117, -17.56042321,
> 5.10059901, -7.97251117, 18.40791387, 42.93339233,
> 11.01881990, -17.56042321, 42.93339233, 160.07749441,
> -2.03282321, 2.77364997, -5.10059901, -11.01881990,
> 2.77364997, -4.19157832, 7.97251117, 17.56042321,
> -5.10059901, 7.97251117, -18.40791387, -42.93339233,
> -11.01881990, 17.56042321, -42.93339233, -160.07749441,
> -0.00000000, -0.00000000, -0.00000000, -0.00000000, -1.70966084,
> -0.00000000, -0.00000000, 0.00000000, -0.00000000, 0.00000000,
> -0.00000000,
>
>
>
>
> 0.85483042,
> -0.85483042,
> END_DATA,
> ~
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--
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 u-pem.fr
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