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

Download Pr_LFDFT.run

Application of the Ligand Field DFT approach for the atomic Pr 4f2 → Pr 4f1 5d1 transition.

First an average of configuration calculation (AOC) is performed for the 4f2 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.

$ADFBIN/adf <<eor Atoms Pr 0.000000 0.000000 0.000000 End Occupations 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 End input eor  Next 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 4f1 5d1 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 Occupations 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 End input eor  Next 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 4f2 → Pr 4f1 5d1. 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