SCM: Examples

TlH: Spin-Orbit SFO analysis

Sample directory: adf/TlH_SO_analysis/

Application of the Spin-Orbit relativistic option (using double-group symmetry) to TlH with a detailed analysis of the spinors in terms of SFOs (Symmetrized Fragment Orbitals).

In order to get the population analysis, one should have one scalar relativistic fragment, which is the whole molecule. The SFOs in this case are the scalar relativistic orbitals, which are already orthonormal, because one has only one fragment which is the whole molecule.

First the relativistic fragment is made, including the create of the atoms:

$ADFBIN/dirac -n1  < $ADFRESOURCES/Dirac/Tl
$ADFBIN/dirac -n1  < $ADFRESOURCES/Dirac/H
mv TAPE12 t12.rel

$ADFBIN/adf  <<eor
create Tl  file=$ADFRESOURCES/ZORA/TZ2P/Tl
xc
  LDA vwn
  GGA  becke perdew
end
relativistic scalar zora
corepotentials  t12.rel  &
Tl     1
H      2
end
end input
eor
mv TAPE21 t21.Tl

$ADFBIN/adf  <<eor
create H  file=$ADFRESOURCES/ZORA/TZ2P/H
xc
  LDA vwn
  GGA  becke perdew
end
relativistic scalar zora
corepotentials  t12.rel  &
Tl     1
H      2
end
end input
eor
mv TAPE21 t21.H


$ADFBIN/adf  <<eor
title   TlH, scalar relativistic zora

integration 6.0

relativistic scalar zora
corepotentials  t12.rel  &
Tl    1
H     2
end

ATOMS
Tl       0.0             0.0             0.0
H        0.0             0.0             1.870
end

fragments
Tl t21.Tl
H  t21.H
end

xc
  LDA vwn
  GGA  becke perdew
end

EPRINT
SFO eig ovl
END

end input
eor

mv TAPE21 t21.TlH

In order to get the population analysis, one should have one scalar relativistic fragment, which is the whole molecule, which is TlH in this case.

$ADFBIN/adf  <<eor
title   TlH from fragment TlH,  with SpinOrbit coupling

integration 6.0

relativistic spinorbit zora
corepotentials  t12.rel  &
Tl    1
H     2
end

ATOMS
Tl       0.0             0.0             0.0    f=TlH
H        0.0             0.0             1.870  f=TlH
end

fragments
TlH     t21.TlH
end

xc
  LDA vwn
  GGA  becke perdew
end

EPRINT
SFO eig ovl
END

end input
eor

The output gives something like:

 =======================
 Double group symmetry :  ***   J1/2  ***
 =======================

                                       ===  J1/2:1 ===

 Spinors expanded in SFOs
....
Spinor:             21               22               23               24
 occup:            1.00             1.00             1.00             0.00
 ------            ----             ----             ----             ----
 SFO SIGMA
   13.alpha:   0.7614+0.0000i   0.0096+0.0000i   0.0052+0.0000i  -0.0006+0.0000i
   14.alpha:   0.0154+0.0000i  -0.9996+0.0000i   0.0208+0.0000i  -0.0077+0.0000i
   15.alpha:  -0.0146+0.0000i   0.0185+0.0000i   0.9849+0.0000i   0.1625+0.0000i
 SFO PI:x
    8.beta :   0.4578+0.0000i   0.0091+0.0000i   0.0112+0.0000i   0.0030+0.0000i
    9.beta :   0.0005+0.0000i  -0.0074+0.0000i  -0.1119+0.0000i   0.6910+0.0000i
 SFO PI:y
    8.beta :   0.0000+0.4578i   0.0000+0.0091i   0.0000+0.0112i   0.0000+0.0030i
    9.beta :   0.0000+0.0005i   0.0000-0.0074i   0.0000-0.1119i   0.0000+0.6910i
....

Left out are a lot of small numbers. The meaning is that a spinor of J_z=1/2 symmetry can have SIGMA and PI character, for example, the 21st spinor with occupation number 1.0, is approximately
(21 J_z=1/2) = 0.76 (13 SIGMA alpha) + 0.46 (8 PI:x beta) + i 0.46 (8 PI:y beta)

Next in the SFO contributions per spinor the real and imaginary spin alpha part and real and imaginary spin beta part are all summed together to give a percentage of a certain SFO. are summed. For example the 21st spinor has almost 60% (13 SIGMA) character.

 SFO contributions (%) per spinor
 Spinor:      21     22     23     24 
 occup:      1.00   1.00   1.00   0.00
 ------      ----   ----   ----   ----
 SFO SIGMA
     13:    57.97   0.01   0.00   0.00
     14:     0.02  99.92   0.04   0.01
     15:     0.02   0.03  97.01   2.64
 SFO PI:x
      8:    20.96   0.01   0.01   0.00
      9:     0.00   0.01   1.25  47.75
 SFO PI:y
      8:    20.96   0.01   0.01   0.00
      9:     0.00   0.01   1.25  47.75