# Example: Ligand Field DFT: f-d transitions in Pr 3+¶

Download Pr_LFDFT.run

#!/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="$AMSHOME/examples/adf/Pr_LFDFT/LFDFT" export SCM_LFDFT AMS_JOBNAME=f2$AMSBIN/ams <<eor
System
atoms
Pr        0.000000    0.000000    0.000000
end
end

irrepoccupations
A 54 0.2857143 0.2857143 0.2857143 0.2857143 0.2857143 0.2857143 0.2857143
end
basis
core none
type ZORA/TZ2P+
end
numericalquality good
relativity
level scalar
formalism ZORA
end
symmetry nosym
EndEngine
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 adf.rkf.

$AMSBIN/lfdft <<eor adffile f2.results/adf.rkf nshel 1 nlval 4 3 MOind 28 29 30 31 32 33 34 soc 1 eor rm logfile # Next an average of configuration calculation (AOC) is performed for the 4f^1 # 5d^1 electron configuration, where 1 electron is equally distributed over the # 7 orbitals that have the most dominant Pr 4f character, and 1 electron is # equally distributed over the 7 orbitals that have the most dominant Pr 5d # character. Depending on the electron configuration this might be a non-trivial # task. AMS_JOBNAME=f1d1$AMSBIN/ams <<eor
System
atoms
Pr        0.000000    0.000000    0.000000
end
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
basis
core none
type ZORA/TZ2P+
end
numericalquality good
relativity
level scalar
formalism ZORA
end
symmetry nosym
EndEngine
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 adf.rkf.

$AMSBIN/lfdft <<eor adffile f1d1.results/adf.rkf nshel 2 nlval1 4 3 nlval2 5 2 MOind1 28 29 30 31 32 33 34 MOind2 35 36 37 38 39 soc 1 1 eor rm logfile # Next excitation energies are calculated for exciting from the ground state of # the Pr 4f^2 -> Pr 4f^1 5d^1. Input for lfdft_tdm are the 2 .t21 files that were # calculated previously. Results of the excitation energies are added on the # adf.rkf file belonging to state2.$AMSBIN/lfdft_tdm <<eor