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