Computational Details of Calcium Dimer
Potentials dissociating to the 1S+1P
and 1S+3P asymptotes
The multiconfiguration basis set for the calculation of the excited of the
Ca2 molecule is based on the Dirac-Fock atomic orbitals the
[1s2 2s2 2p6 3s2] 3p6
4s2 ground configuration with additional Dirac-Fork excited 3d and
4p orbitals and Sturmian orbitals labeled 5s and 5p. The closed shells
1s22s22p63s2 +
1s22s22p63s2
form the core of the molecule and no excitations from these shells will be
allowed. The 3p6, 4s2, 3d, and 4p orbitals are valence
orbitals and single and double occupation and excitation from these orbitals
occur. Covalent and ionic configurations are constructed by distributing
electrons from the valence orbitals in all allowed ways over the orbitals.
There are 393 nonrelativistic molecular configurations and 2290 relativistic
configurations. The potential curves are calculated based on the relativistic
Hamiltonian in order to take into account the spin-orbit splittings of the
excited states. Non relativistic labels are also shown. The zero of energy is
located at the dissociation limit of the ground state of Ca2.
Potentials dissociating to the 3P+3P asymptotes.
The multiconfiguration basis set for the calculation of the highly excited state
potentials dissociating to the 3P+3P asymptotes of the
Ca2 molecule is based on the Dirac-Fock atomic orbitals belonging to
the [1s2 2s2 2p6 3s2] 4s4p
configuration with an additional Dirac-Fock 3d orbital and Sturmian orbitals
labeled 5s and 5p. The closed shells
1s2 2s22p63s2 +
1s2 2s22p63s2 form the core of the
molecule and no excitations from these shells will be allowed. The
3p6, 4s2, 4p, and 3d orbitals are valence orbitals and
single and double occupation and excitation from these orbitals occur. Covalent
and ionic configurations are constructed by distributing electrons from the
valence orbitals in all allowed ways over the orbitals. This leads to the same
number of molecular configuration as in the calculation for the lower lying
excited states. Again the potential curves are calculated based on the
relativistic Hamiltonian in order to take into account the spin-orbit
splittings of the excited states.
The number of relativistic potentials  g/u± = 0, 1, 2, 3, 4 dissociating
to the 3P+3P asymptotes is now significantly larger. The
zero of energy is again at the dissociation limit of the ground state of
Ca2. Some of the 0+ and 0- curves are
degenerate on the scale of the figures.
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