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.
$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