Example: Core excitation energies: TiCl4¶

Download TiCl4_CoreExci.run

#! /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

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# == 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