Example: Ligand Field DFT: f-d transitions in Pr 3+¶
#!/bin/sh
# Application of the Ligand Field DFT approach for the atomic Pr 4f^2 -> Pr 4f^1
# 5d^1 transition.
# First an average of configuration calculation (AOC) is performed for the 4f^2
# electron configuration, where 2 electrons are equally distributed over the 7
# orbitals that have the most dominant Pr 4f character. Depending on the
# electron configuration this might be a non-trivial task.
SCM_LFDFT="$ADFHOME/examples/adf/Pr_LFDFT/LFDFT"
export SCM_LFDFT
$ADFBIN/adf <<eor
Atoms
Pr 0.000000 0.000000 0.000000
End
IrrepOccupations
A 54 0.2857143 0.2857143 0.2857143 0.2857143 0.2857143 0.2857143 0.2857143
End
Symmetry nosym
Basis
type ZORA/TZ2P+
core none
End
relativistic scalar zora
numericalquality good
eor
# Next the an LFDFT calculation is performed including spin-orbit coupling (soc
# 1). In this case there is 1 shell, and the nlval for 4f is '4 3'. The MO
# indices should be the fractionally occupied levels of the AOC calculation (28
# 29 30 31 32 33 34). Results are added on TAPE21.
$ADFBIN/lfdft <<eor
nshel 1
nlval 4 3
MOind 28 29 30 31 32 33 34
soc 1
eor
mv TAPE21 Pr_f2.t21
rm logfile
# Next an average of configuration calculation (AOC) is performed for the 4f^1
# 5d^1 electron configuration, where 1 electron is equally distributed over the
# 7 orbitals that have the most dominant Pr 4f character, and 1 electron is
# equally distributed over the 7 orbitals that have the most dominant Pr 5d
# character. Depending on the electron configuration this might be a non-trivial
# task.
$ADFBIN/adf <<eor
Atoms
Pr 0.000000 0.000000 0.000000
End
IrrepOccupations
A 54 0.1428571 0.1428571 0.1428571 0.1428571 0.1428571 0.1428571 0.1428571 0.2 0.2 0.2 0.2 0.2
End
Symmetry nosym
Basis
type ZORA/TZ2P+
core none
End
relativistic scalar zora
numericalquality good
eor
# Next the an LFDFT calculation is performed including spin-orbit coupling for
# both 4f and 5d (soc 1 1). In this case there are 2 shells, and the nlval for
# 4f is '4 3', and for 5d '5 2'. The MO indices should be the fractionally
# occupied levels of the AOC calculation for 4f (28 29 30 31 32 33 34), and for
# 5d (35 36 37 38 39). Results are added on TAPE21.
$ADFBIN/lfdft <<eor
nshel 2
nlval1 4 3
nlval2 5 2
MOind1 28 29 30 31 32 33 34
MOind2 35 36 37 38 39
soc 1 1
eor
mv TAPE21 Pr_f1d1.t21
rm logfile
# Next excitation energies are calculated for exciting from the ground state of
# the Pr 4f^2 -> Pr 4f^1 5d^1. Input for lfdft_tdm are the 2 .t21 files that were
# calculated previously. Results of the excitation energies are added on the
# .t21 file belonging to state2.
$ADFBIN/lfdft_tdm <<eor
state1 Pr_f2.t21
state2 Pr_f1d1.t21
eor