Example: X-Ray Absorption and Emission Quadrupole Oscillator strengths at the Cl K-edge: TiCl4¶
#! /bin/sh
# Calculation of the 1s Cl core excitation energies of TiCl4. Both X-Ray
# Emission (XES keyword) and X-Ray absorption (XAS keyword in EXCITATION key)
# are calculated. The individual (zeroth and higher order) oscillator strength
# components to the total oscillator strengths will be printed
# (ALLXESQUADRUPOLE, ALLXASQUADRUPOLE).
# In order to calculate a 1s-orbital that is localized on one of the Cl atoms, a
# frozen core approach is used on the other Cl atoms, such that there is only
# one Cl 1s-orbital, which will remain localized in the molecule.
# In order to get information of the population analysis on all core orbitals, a
# large negative value was included as argument for the orbpoper subkey of the
# block key EPRINT. This orbital analysis shows that the 2 A1 orbital is indeed
# the 1s Cl orbital, see subkey corehole of block key XES, and subkey
# useoccupied of block key MODIFYEXCITATION.
"$ADFBIN/adf" <<eor
TITLE TiCl4 X-Ray Absorption and Emission Quadrupole Oscillator strengths at the Cl K-edge
ATOMS
1 Ti 0.0000 0.0000 0.0000
2 Cl 0.0000 0.0000 2.2930
3 Cl.1 1.0809 -1.8722 -0.7643
4 Cl.1 -2.1618 0.0000 -0.7643
5 Cl.1 1.0809 1.8722 -0.7643
END
SYMMETRY C(3V)
BASIS
type TZP
core None
createoutput None
Cl.1 $ADFRESOURCES/TZP/Cl.2p
END
XC
GGA Becke Perdew
END
EPRINT
eigval 1000 1000
orbpoper -10000 100
End
RELATIVISTIC Scalar ZORA
SCF
iterations 200
END
XES
COREHOLE A1 2
ALLXESQUADRUPOLE
END
MODIFYEXCITATION
UseOccupied
A1 2
SubEnd
END
EXCITATIONS
davidson
End
ONLYSING
lowest 10
XAS
ALLXASQUADRUPOLE
END
eor
mv TAPE21 restart.t21
rm logfile
# In the second example, to test gauge dependency, the molecule is shifted 100
# Angstrom in the z-direction.
"$ADFBIN/adf" <<eor
TITLE TiCl4 X-Ray Absorption and Emission Quadrupole Oscillator strengths at the Cl K-edge shifted 100Ang in z-direction
ATOMS
1 Ti 0.0000 0.0000 100.0000
2 Cl 0.0000 0.0000 102.2930
3 Cl.1 1.0809 -1.8722 99.2357
4 Cl.1 -2.1618 0.0000 99.2357
5 Cl.1 1.0809 1.8722 99.2357
END
SYMMETRY C(3V)
BASIS
type TZP
core None
createoutput None
Cl.1 $ADFRESOURCES/TZP/Cl.2p
END
XC
GGA Becke Perdew
END
EPRINT
eigval 1000 1000
orbpoper -10000 100
End
RELATIVISTIC Scalar ZORA
SCF
iterations 200
END
XES
COREHOLE A1 2
ALLXESQUADRUPOLE
END
MODIFYEXCITATION
UseOccupied
A1 2
SubEnd
END
EXCITATIONS
davidson
End
ONLYSING
lowest 10
XAS
ALLXASQUADRUPOLE
END
RESTART
File restart.t21
noGEO True
noEXC True
END
eor
rm TAPE21
rm restart.t21
rm logfile