How
would we combine atomic orbitals to make molecular orbitals for
diatomic molecules such as HF? Would the 2s hydrogen orbital interact
with the 2s orbital of fluorine, and the 2P of hydrogen with the
2p of fluorine? No, because the energies of orbitals with corresponding
quantum numbers in H and F are very different. The increased nuclear
charge of +9 on F, compared to +1 on H, pulls on the electrons in
all the fluorine quantum levels and makes them more stable (lower
energy). The is orbital of fluorine is so much lower in energy than
the is of hydrogen that they cannot possibly interact. The outer
occupied orbital in F and the is H orbital are the ones that are
of similar energy. The first ionization energy of each kind of atom
is the energy needed to remove one electron from an outer orbital:
the is of hydrogen, and the 2p of fluorine. The first ionization
energy of hydrogen is 313 kcal mole,
and that of fluorine is 402 kcal mole,
so the 2p orbitals in F are approximately 89 kcal mole
lower in energy than the is orbital in H. These are the orbitals
that are similar enough in energy to combine, and their relative
energies are shown at the left and right of the energy-level diagram
in the margin. The 2s orbital of fluorine is off scale at the bottom
of the diagram, and the is is lower still. Molecular orbitals for
HF are obtained by combining the 1s of H with the 2p of F.