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/usr/share/psi4/samples/scf-occ/input.dat is in psi4-data 1:1.1-5.

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#! force occupations in scf

molecule sodium {
1 1
Na
}


activate(sodium)
set basis STO-3G
set reference rhf
set guess core
cation_e = energy('scf')

molecule sodium {
0 2
Na
}

activate(sodium)
set basis STO-3G
set reference rohf
set guess read
set docc [ 2, 0, 0, 0, 0, 1, 1, 1 ]
set socc [ 1, 0, 0, 0, 0, 0, 0, 0 ]
neutral_e = energy('scf')


molecule {
0 2
Li
}

set basis STO-3G
set reference rohf
set guess sad
set docc [ 1, 0, 0, 0, 0, 0, 0, 0 ]
set socc [ 1, 0, 0, 0, 0, 0, 0, 0 ]
li_e = energy('scf')