[molpro-user] LS Integral format via MATROP

[Murphy, Paul]

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,
~
________________________________

Founded in 1821, Heriot-Watt is a leader in ideas and solutions. With campuses and students across the entire globe we span the world, delivering innovation and educational excellence in business, engineering, design and the physical, social and life sciences.

The contents of this e-mail (including any attachments) are confidential. If you are not the intended recipient of this e-mail, any disclosure, copying, distribution or use of its contents is strictly prohibited, and you should please notify the sender immediately and then delete it (including any attachments) from your system.