1a)

HF is a heteronuclear atom which exhibits a polar covalent bond. The orbitals no

longer have equal density on each atom.
i)
ii)

either bonding, non-bonding, or antibonding

either Hlocalized, primarily H-character, primarily F-character, or Flocalized.
To arrive at your answers, consider the nature and relative energies of the
atomic orbitals that overlap to form each molecular orbital.
a)

1 i) non Bonding. ii) Primarily F2s in character. HF is a heteronuclear atom which

exhibits a polar covalent bond. The orbitals no longer have equal density on each
atom. The high fluorine localization of this orbital is a consequence of the high
electronegativity of fluorine.

2 i) Bonding ii) F-localized. Has both H1s and F2p character. HF is a

heteronuclear atom which exhibits a polar covalent bond. The orbitals no longer
have equal density on each atom. The high fluorine localization of this orbital is a
consequence of the high electronegativity of fluorine. There is s AO p AO overlap
in this molecular orbital.
1 i) nonbonding ii) Primarily F-character - Fluorine 2p in character. These orbitals
exist in the fluorine atom. They analogous to 2p fluorine AOs. They are not involved
in bonding. They arent involved in anti-bonding either. They are non-bonding.

Fluorine 2pX & 2pY . Run perpendicular to H-F axis Z. Do not overlap S-orbital. Do
not participate in anti-bonding with it either. Therefore nonbonding.
3 i) anti-bonding ii) H-localized. The H1S AO has relatively high energy when
compared to the fluorine orbitals. Therefore, the hydrogens 1S orbital contributes
predominantly to the high-energy antibonding MO.

b)
1 and 2 MOs are F-localized due to the electronegativity of F in the MO
orbital
1 - is non-bonding but is fluorine 2p in character. Therefore, eoccupying this MO will inhabit the 2 p-orbitals of fluorine.
3 Antibonding, unoccupied, LUMO. Primarily H 1s AO orbital
characteristic. Since unoccupied no effect on molecular polarity. Antibonding MO - would destable molecule if occupied.
3/3 occupied MOs have the majority of charge based on the fluorine. Any
given molecule has characteristics of an average of the sum of its MOs.
Therefore, the entire H-F molecule is polar because 3/3 occupied MOs
exhibit electron density on the fluorine.

c) Fluorine 2pX & 2pY . Run perpendicular to H-F axis Z. Do not overlap
S-orbital. Do not anti-overlap it either. Therefore nonbonding.
d) MO description completely agrees. Has 1 bonding pair localized to the
electronegative fluorine and 3 electron pairs based on the fluorine which
do not participate in bonding.
2 e- enter the 2 orbital, forming a bond between H & F atoms. Polar
bond is localized on F atom.
2 e- enter into the 1 orbital which is largely non-bonding and confined to
F atom.
4 e- enter the 1-pi orbital which are non-bonding and confined to the F
atom.
The MO prediction does not agree with the fact that Lewis structure
suggests nominally equivalent electrons localized on the fluorine. The
electrons localized on the fluorine occupy different energy levels. MO &
VSEPR do however agree in that the number of bonding and F-localized
nonbonding pairs are numerically equivalent.
2)

a) Carbon has 4 valence e-. The photoelectron spectrum of methane

shows a peak at 13eV and a peak approximately (1/3) of the size at 23 eV.
VSEPR assumes all valenec bonds are equal in energy. This is not the case
in this photoelectron spectrum. 3 valence bonds of carbon lie in one
energy level and one lies in an energy level in which more energy is
needed to break the bond. This is to say that, in methane, 3 pairs of
bonding e- occupy 3 degenerate orbitals and one pair of bonding electrons
occupies a bonding s-orbital which is harder to extract
Carbon has four valence electrons. One in a 2s orbital and 3 in 2p orbitals.