#! /bin/sh

# Calculation of the 2p Ti and 2p Cl core excitation energies of TiCl4

# The state selective method (key SELECTEXCITATION) can be used to calculate
# core excitation energies. 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 TiCl4 TD-DFT spinorbit relativistic 2p Cl core excitations single orbital transitions

Units
 LENGTH BOHR
End

Atoms
 Ti 0.       0.        0.    
 Cl    2.36754     2.36754     2.36754   
 Cl   -2.36754    -2.36754     2.36754   
 Cl    2.36754    -2.36754    -2.36754   
 Cl   -2.36754     2.36754    -2.36754   
End
SYMMETRY T(D)  

EPRINT
 eigval 1000 1000
End

XC
 GGA LB94
End

relativistic spinorbit zora

SelectExcitation
 UseOccRange -20.0 -16.0
 UseScaledZORA
END
Excitations
 SingleOrbTrans
 allowed
 lowest 40
 kfwrite 0
End

Basis
 Type DZ
 Core None
End

BeckeGrid
 Quality good
End

EOR

rm TAPE21
rm logfile


# == An example with the key MODIFYEXCITATION ==

# In this example, the 12 lowest singlet-singlet excitation energies of T2
# symmetry are calculated, the dipole allowed excitations. This can also be
# achieved using the ALLOWED subkey in the key Excitation.

# In this example only excitations from the 2t2 -orbital are included (see the
# key MODIFYEXCITATION), an almost pure 2p core orbital of titanium. The orbital
# energies of the uninteresting other occupied orbitals are artificially changed
# to a large negative value (-1d6 hartree).


$ADFBIN/adf <<EOR
Title TiCl4 TD-DFT scalar relativistic 2p Ti core excitations

Units
 LENGTH BOHR
End

Atoms
 Ti 0.       0.        0.    
 Cl    2.36754     2.36754     2.36754   
 Cl   -2.36754    -2.36754     2.36754   
 Cl    2.36754    -2.36754    -2.36754   
 Cl   -2.36754     2.36754    -2.36754   
End
SYMMETRY T(D)  

EPRINT
 eigval 1000 1000
End

XC
 GGA LB94
End

relativistic scalar zora

ModifyExcitation
 UseOccupied
  T2 2
 SubEnd
 UseScaledZORA
END

Excitations
 ONLYSING
 davidson
  T2 12
 SubEnd
End

Basis
 Type DZ
 Core None
End

BeckeGrid
 Quality good
End

EOR

rm TAPE21
rm logfile


# In this example the 2p Cl core excitation energies of TiCl4 are calculated.

# In this example only excitations from occupied orbitals are considered which
# have orbital energies between -8 and -6 hartree, namely the 5a1, 1e, 1t1,
# 4t2, and 5t2 orbitals, which are almost pure 2p core orbitals of chlorine.
# The orbital energies of the uninteresting other occupied orbitals are again
# artificially changed to a large negative value (-1d6 hartree).

$ADFBIN/adf <<EOR
Title TiCl4 TD-DFT scalar relativistic 2p Cl core excitations

Units
 LENGTH BOHR
End

Atoms
 Ti 0.       0.        0.    
 Cl    2.36754     2.36754     2.36754   
 Cl   -2.36754    -2.36754     2.36754   
 Cl    2.36754    -2.36754    -2.36754   
 Cl   -2.36754     2.36754    -2.36754   
End
SYMMETRY T(D)  

EPRINT
 eigval 1000 1000
End

XC
 GGA LB94
End

relativistic scalar zora

ModifyExcitation
 UseOccRange -8.0 -6.0
 UseScaledZORA
END

Excitations
 allowed
 lowest 50
End

Basis
 Type DZ
 Core None
End

BeckeGrid
 Quality good
End

EOR

rm TAPE21
rm logfile


# Another possibility is the use of the subkey OccVirtRange:

$ADFBIN/adf <<EOR
Title TiCl4 TD-DFT scalar relativistic 2p Cl core excitations

Units
 LENGTH BOHR
End

Atoms
 Ti 0.       0.        0.    
 Cl    2.36754     2.36754     2.36754   
 Cl   -2.36754    -2.36754     2.36754   
 Cl    2.36754    -2.36754    -2.36754   
 Cl   -2.36754     2.36754    -2.36754   
End
SYMMETRY T(D)  

EPRINT
 eigval 1000 1000
End

XC
 GGA LB94
End

relativistic scalar zora

ModifyExcitation
 UseOccVirtRange 7.0 100.0
 UseScaledZORA
END

Excitations
 allowed
 lowest 50
End

Basis
 Type DZ
 Core None
End

BeckeGrid
 Quality good
End

EOR

rm TAPE21
rm logfile



$ADFBIN/adf <<EOR
Title TiCl4 TD-DFT scalar relativistic 2p Ti core excitations

Units
 LENGTH BOHR
End

Atoms
 Ti 0.       0.        0.    
 Cl    2.36754     2.36754     2.36754   
 Cl   -2.36754    -2.36754     2.36754   
 Cl    2.36754    -2.36754    -2.36754   
 Cl   -2.36754     2.36754    -2.36754   
End
SYMMETRY T(D)  

EPRINT
 eigval 1000 1000
End

XC
 GGA LB94
End

relativistic scalar zora

SelectExcitation
 UseOccupied
  T2 2
 SubEnd
 UseScaledZORA
END

Excitations
 ONLYSING
 davidson
  T2 12
 SubEnd
End

Basis
 Type DZ
 Core None
End

BeckeGrid
 Quality good
End

EOR

rm TAPE21
rm logfile

$ADFBIN/adf <<EOR
Title TiCl4 TD-DFT scalar relativistic 2p Cl core excitations

Units
 LENGTH BOHR
End

Atoms
 Ti 0.       0.        0.    
 Cl    2.36754     2.36754     2.36754   
 Cl   -2.36754    -2.36754     2.36754   
 Cl    2.36754    -2.36754    -2.36754   
 Cl   -2.36754     2.36754    -2.36754   
End
SYMMETRY T(D)  

EPRINT
 eigval 1000 1000
End

XC
 GGA LB94
End

relativistic scalar zora

SelectExcitation
 UseOccVirtRange 7.0 100.0
 UseScaledZORA
END

Excitations
 allowed
 lowest 25
End

Basis
 Type DZ
 Core None
End

BeckeGrid
 Quality good
End

EOR

rm TAPE21
rm logfile