Example: (Core) Excitation energies including spin-orbit coupling: Ne¶

Download Ne_exciso.run and Download Ne_CoreExci.run

Calculation of the (core) excitation energies of Ne including spin-orbit coupling.

The state selective method (key SELECTEXCITATION) can be used to reduce the computational costs of, for example, core excitation energies. In this scheme a guess vector for the orbital transition has to be provided. It should be used in combination with the Davidson method to calculate excitation energies. An overlap criterion is used to follow the wanted eigenvector. This key can also be used in case of spin-orbit coupling. The use of the key SELECTEXCITATION is similar as the use of the key MODIFYEXCITATION. However, the key SELECTEXCITATION can not be used in combination with the key MODIFYEXCITATION. In the state selective method (key SELECTEXCITATION) the one-electron excited state configuration space remains complete, whereas it is reduced in case the scheme with the MODIFYEXCITATION key.

$ADFBIN/adf << eor
Title Ne
Atoms
  Ne .0000  .0000  0.0000
End
Basis
 Type QZ4P
End
relativistic scalar zora
symmetry d(8h)
NumericalQuality Good
xc
 model SAOP
end
Excitations
 lowest 10
End
*ModifyExcitation
   UseOccupied
    A1.g 1
   SubEnd
   UseScaledZORA
  END
*
End input
eor

mv TAPE21 Frag.t21
rm logfile TAPE21

$ADFBIN/adf << eor
Title Ne spin-orbit
Atoms
  Ne .0000  .0000  0.0000  f=Frag
End
relativistic spinorbit zora
symmetry d(8h)
xc
 model SAOP
end
NumericalQuality Good
Excitations
 lowest 12
End
*SelectExcitation
   UseOccupied
    E1/2.g 1
   SubEnd
   UseScaledZORA
  END
*
Fragments
 Frag Frag.t21
End
STCONTRIB
End input
eor

The difference between the core excitation calculation and the standard excitation is the extra subkey MODIFYEXCITATION or SELECTEXCITATION in the core excitation calculation (in italic).

ADF can not handle ATOM and linear symmetries in excitation calculations. Therefore a subsymmetry is used, in this case symmetry d(8h).

A relatively large QZ4P basis set is used, which is still insufficient for excitations to Rydberg-like orbitals, one needs more diffuse functions.

The key STCONTRIB is used, which will give a composition of the spin-orbit coupled excitation in terms of singlet-singlet and singlet-triplet scalar relativistic excitations. In order to use the key STCONTRIB the scalar relativistic fragment should be the complete molecule.

In this case the key MODIFYEXCITATION or SELECTEXCITATION takes care that only excitations from the occupied 1s-orbital (spinor) are included. In symmetry d(8H) the 1s-orbital (spinor) is of A1.g (E1/2.g) symmetry.