# Example: Core excitation energies: TiCl4¶

```
#! /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.
AMS_JOBNAME=SOT $AMSBIN/ams <<eor
System
atoms [Bohr]
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
end
Task SinglePoint
Engine ADF
title TiCl4 TD-DFT spinorbit relativistic 2p Cl core excitations single orbital transitions
beckegrid
quality good
end
eprint
eigval 1000 1000
end
excitations
allowed
kfwrite 0
lowest 40
singleorbtrans
end
basis
core None
type DZ
CreateOutput Yes
end
relativity
level spin-orbit
formalism ZORA
end
selectexcitation
useoccrange -20.0 -16.0
usescaledzora
end
symmetry T(D)
xc
gga LB94
end
EndEngine
eor
# == 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).
AMS_JOBNAME=T2 $AMSBIN/ams <<eor
System
atoms [Bohr]
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
end
Task SinglePoint
Engine ADF
title TiCl4 TD-DFT scalar relativistic 2p Ti core excitations
beckegrid
quality good
end
eprint
eigval 1000 1000
end
excitations
davidson
T2 12
end
onlysing
end
modifyexcitation
useoccupied
T2 2
end
usescaledzora
end
basis
core None
type DZ
CreateOutput Yes
end
relativity
level scalar
formalism ZORA
end
symmetry T(D)
xc
gga LB94
end
EndEngine
eor
# 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).
AMS_JOBNAME=OccRange $AMSBIN/ams <<eor
System
atoms [Bohr]
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
end
Task SinglePoint
Engine ADF
title TiCl4 TD-DFT scalar relativistic 2p Cl core excitations
beckegrid
quality good
end
eprint
eigval 1000 1000
end
excitations
allowed
lowest 50
end
modifyexcitation
useoccrange -8.0 -6.0
usescaledzora
end
basis
core None
type DZ
CreateOutput Yes
end
relativity
level scalar
formalism ZORA
end
symmetry T(D)
xc
gga LB94
end
EndEngine
eor
# Another possibility is the use of the subkey OccVirtRange:
AMS_JOBNAME=OccVirt $AMSBIN/ams <<eor
System
atoms [Bohr]
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
end
Task SinglePoint
Engine ADF
title TiCl4 TD-DFT scalar relativistic 2p Cl core excitations
beckegrid
quality good
end
eprint
eigval 1000 1000
end
excitations
allowed
lowest 50
end
modifyexcitation
useoccvirtrange 7.0 100.0
usescaledzora
end
basis
core None
type DZ
CreateOutput Yes
end
relativity
level scalar
formalism ZORA
end
symmetry T(D)
xc
gga LB94
end
EndEngine
eor
AMS_JOBNAME=SelectT2 $AMSBIN/ams <<eor
System
atoms [Bohr]
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
end
Task SinglePoint
Engine ADF
title TiCl4 TD-DFT scalar relativistic 2p Ti core excitations
beckegrid
quality good
end
eprint
eigval 1000 1000
end
excitations
davidson
T2 12
end
onlysing
end
basis
core None
type DZ
CreateOutput Yes
end
relativity
level scalar
formalism ZORA
end
selectexcitation
useoccupied
T2 2
end
usescaledzora
end
symmetry T(D)
xc
gga LB94
end
EndEngine
eor
AMS_JOBNAME=SelectOccVir $AMSBIN/ams <<eor
System
atoms [Bohr]
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
end
Task SinglePoint
Engine ADF
title TiCl4 TD-DFT scalar relativistic 2p Cl core excitations
beckegrid
quality good
end
eprint
eigval 1000 1000
end
excitations
allowed
lowest 25
end
basis
core None
type DZ
CreateOutput Yes
end
relativity
level scalar
formalism ZORA
end
selectexcitation
useoccvirtrange 7.0 100.0
usescaledzora
end
symmetry T(D)
xc
gga LB94
end
EndEngine
eor
```