Homonuclear Diatomic Molecules:

Second-Period Atoms
• The LCAO method was invented to construct approximate molecular orbitals
directly from the Hartree atomic orbitals for the specific atoms in the molecule,
guided by molecular symmetry and chemical intuition.
• Constructing the approximate MOs and recognizing how their electron density is
distributed over the entire network of fixed nuclei are the key tools for describing
molecular structure and bonding.
• Imagine that two Li atoms in their ground-state electronic configurations
(1s)2(2s)1 approach each other.
 The 2s AOs will interact to produce MOs (bonding and anti-bonding MOs but
larger in size, σ2s).
 The 1s orbitals will combine to form σ1s bonding and anti-bonding MOs.
 Then the Li2 molecule would have the electron configuration:
(σg1s)2(σu1s*)2(σg2s)2 .
 In a similar way, Be2 has the configuration (σg1s)2(σu1s*)2(σg2s)2(σu2s*)2 .
• Because of the very poor spatial overlap of the 1s AOs, however, it is typical to see
those electrons listed as simply remaining in the two 1s AOs. They are often
omitted from the LCAO-MO correlation diagram.
• Constructing the approximate MOs from the valence AOs only (subtract off the
core electrons).
• In the remainder of Period 2 from B to Ne, we must consider the possibility that
the 2p AOs will interact with each other and also with the 2s AOs.
 The relative orientation of the two orbitals will strongly influence the
formation of MOs (2p AOs are not spherical).
 Two dumbbell shapes interacting end-to-end will produce a different result
than side-to-side or end-to-side. Moreover, the difference in phase (the sign
of the wave function) of the two lobes will strongly influence the result.

• How to construct the MOs for second-period atoms in a systematic way:

1. Two atomic orbitals contribute significantly to bond formation only if their
atomic energy levels are very close to one another (1s ↔ 2s or 2p)
2. Two atomic orbitals on different atoms contribute significantly to bond
formation only if they overlap significantly.
• Two orbitals overlap significantly if both have appreciable amplitudes over the
same region of space. The net overlap may be positive, negative, or zero,
depending on the relative amplitudes and phases of orbitals involved in the
overlap region.
• If this is zero, the two orbitals are said to have zero overlap. The 2s orbital on atom
A has zero overlap with the 2px or the 2py orbital on atom B (defining the z axis as
the internuclear axis).
• Bonding molecular orbitals arise from positive net overlap (constructive
interference between the wave functions for atomic orbitals), antibonding
molecular orbitals result from negative net overlap (destructive interference
between the wave functions for atomic orbitals).
• Nonbonding molecular orbitals can arise in two ways: a) there may be negligible
overlap of the atomic orbitals because the separation between the nuclei is
greater than the spatial extent of the orbitals or b) regions of positive overlap
cancel regions of negative overlap to give zero net overlap.
• For s orbitals it is rather easy to guess the degree of overlap; the closer the nuclei,
the greater the overlap. If the wave functions have the same phase, the overlap is
positive; if they have opposite phases, the overlap is negative.
 • The overlap between participating atomic orbitals depends strongly on both the
symmetry of the arrangement of the nuclei and on the phases of the orbitals.
• It is important to know whether regions of positive overlap (where the two orbitals
have the same phase) are canceled by regions of negative overlap (where the two
orbitals have opposite phases).

FIGURE 6.14 Overlap of orbitals in

several common combinations. The
magnitude of overlap can be
estimated qualitatively from the
relative size and symmetry of the two
orbitals involved. (Note the radial
nodes in the 2s orbitals, clearly visible
in these images, and the minus sign in
front of each. Table 5.2 and Figure 5.7
show the sign of the 2s wave function
far from the nucleus is negative, but
we are depicting the orbitals in these
linear combinations as red. The red
spherical orbital depicted is the 2s
function in Table 5.2 multiplied by a −1,
so the resulting −2s wave function is
positive far from the nucleus.) For the
2pz orbitals, the z-axis points from left
to right along the internuclear axis.
 Linear Combinations of 2s and 2p Orbitals
• The linear combinations of 2s atomic orbitals give the molecular orbitals,

(or 2sA + 2sB)

• The choice of appropriate combinations of the 2p orbitals is guided by the overlap

arguments and by recalling that the bond axis is the z-axis.

• The π MOs do not have cylindrical symmetry about the internuclear axis. Their
lobes project above and below the x-z (or y-z for πu2py and πg2py*) nodal plane.
• The relative phases of the two AOs determine whether the resulting MO is
bonding or antibonding. Bonding orbitals form through the overlap of wave
functions with the same phase, by constructive interference of electron waves;
antibonding orbitals form through the overlap of wave functions with opposite
phase, by destructive interference of electron waves.
• By considering the symmetry and relative energies of the participating AOs, we
have generated a total of 8 approximate LCAO MOs to accommodate the
electrons in the 2s and 2p AOs. Including the two MOs originating from the 1s AOs,
we now have a total of 10 approximate MOs which can describe diatomic
molecules containing up to 20 electrons, from H2 to Ne2. Each of these is a
simple sum or difference of two AOs.
Energy Levels for the Homonuclear Diatomics, A2
• In second-period diatomic molecules, the 1s orbitals of the two atoms barely
overlap.
• Because the σg1s bonding and σu1s* antibonding orbitals are both doubly
occupied, they have little net effect on bonding properties and need not be
considered.

.
FIGURE 6.17 Energy levels
for the homonuclear
diatomics Li2 through F2.
Notice how the highest
occupied level changes
with the number of
valence electrons. Notice
especially the change
between N2 and O2.
liquid O2
• A simplified physical interpretation relates this result to the extent to which the 2s
and 2pz atomic orbitals can mix while contributing to the molecular orbital.
• The 2s AOs have the right symmetry to mix with 2pz AOs to form a s molecular
orbital directed along the z-axis. In the first part of Period 2, the 2s and 2p are
sufficiently close in energy that mixing occurs and increases the energy of the
nominal σg2p orbital while decreasing the energy of the nominal σg2s orbital.
z

• In the latter part (O and F) the energy separation of 2p and 2s AOs is too great for
mixing to occur. ( )
• Because the 2s and 2px and 2py AOs do not have the right symmetry to mix and
form a π molecular orbital, the energy of the πu2p x(y) MO remains nearly constant
across the period even when the 2s and 2p AOs are close together in energy.

• In the Lewis electron dot diagram for O2, all the electrons appear to be paired.

• The highly reactive nature of molecular oxygen as compared to N2 can be

rationalized as resulting from the readiness of the two π* electrons, unpaired
(paramagnetic) and in different regions of space, to find additional bonding
partners in other molecules.
 Heteronuclear Diatomic Molecules
• Construction of molecular orbitals with different atoms:
 Drop the g and u subscripts on the MO labels (heteronuclear, lack the
inversion symmetry).
 The AOs on the participating atoms now correspond to different energies.

 If atom B is more electronegative than atom A: and

 Molecular orbital correlation diagrams for heteronuclear diatomics start
with the energy levels of the more electronegative atom displaced
downward because that atom attracts valence electrons more strongly than
does the less electronegative atom.
FIGURE 6.21 Correlation diagram for
heteronuclear diatomic molecules, AB.
The atomic orbitals for the more
electronegative atom (B) are displaced
downward because they have lower
energies than those for A. The orbital
filling shown is that for boron monoxide
(BO).
• Example: NO (with 11 valence electrons)

 With eight electrons in bonding orbitals and three in antibonding orbitals,

the bond order of NO is
(paramagnetic)

 The bond energy of NO should be smaller than that of CO, which has one
fewer electron but a bond order of three.
• Example: HF (with large difference in AOs’ energy)
 In the HF molecule, both the 1s and 2s orbitals of the F atom are far too low
in energy to mix with the H 1s orbital. Moreover, the overlap between the H 1s
and F 2s is negligible.
 The net overlap of the H 1s orbital with the 2px or 2py F orbital is zero.
→ nonbonding atomic orbitals (σnb and πnb)
 This leaves only the 2pz orbital of F to mix with the H 1s orbital to give both σ
bonding and σ * anti-bonding orbitals.
M
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M
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.
 Valence Bond Theory and the Electron Pair Bond
• The valence bond (VB) theory was developed to provide a quantum explanation
and justification for the Lewis electron pair model in which the chemical bond is
described as a pair of electrons localized between two atoms (by W. Heitler and F.
London, 1927).
• The valence bond theory constructs a wave function for each individual chemical
bond by assuming that each participating atom arrives with at least one unpaired
electron in an AO.
• The VB wave function for the bond is a product of two one-electron AO wave
functions, each describing an electron localized on one of the atoms. The spins
of the electrons must be paired to satisfy the Pauli exclusion principle.
• VB theory was more widely used than LCAO because it could describe molecular
structure without performing detailed calculations.
• This section presents a qualitative version of VB theory, which easily describes
the structure and geometry of bonds in polyatomic molecules by hand-drawn
sketches.
 Single Bonds: H2
• In H2 molecule (Lewis structure, H:H), the electron configuration of H is (1s)1.
• At very large distances (Figure 6.25(a)), the atoms are independent of each other,
and the wave function describing the pair of them is ϕA(r1A) ϕB(r2B).
• If two objects are independent, their total energy is the sum of the individual
energies, and the wave function for the two of them is the product of the
individual wave functions.
• As the atoms approach closer together so that bond formation is a possibility, it
is reasonable to propose an approximate wave function for the two of them
would take the form

• As the atoms begin to interact strongly, we cannot determine whether electron 1

arrived with proton A and electron 2 with proton B, or vice versa, because the
electrons are indistinguishable (Figure 6.25(b)). To allow for both possibilities we
propose a wave function that is a sum of two of the product forms just
discussed.

• Symmetry requires that c1 = c2 and c1 = − c2 be equally valid choices. We label

these combinations gerade (g) and ungerade (u) respectively to show how each
behaves under inversion symmetry.
• To calculate the probability density for finding electron 1 at r1, no matter where
electron 2 is located, we must square the function and then average over all
possible locations for electron 2. (The same applies to electron 2.)
• Adding these results together gives the total electron density at each point in
space, as a function of the internuclear distance RAB.
• The results for ψgel and ψuel are shown in Figure 6.26a. The wave function ψgel
shows increased electron density between the nuclei (lower energy state &
bond formation), whereas ψuel shows reduced electron density (higher energy
state) between the nuclei.
(b)

• The correct wave function to describe an

electron pair bond in the VB method is

• The wave function for the electron pair

bond in a hydrogen molecule is
constructed by multiplying a 1s orbital
for electron 1 on atom A by a 1s orbital
for electron 2 on atom B and adding the
product to the result of multiplying a 1s
orbital for electron 2 on atom A by a 1s
orbital for electron 1 on atom B and
finally normalizing the resulting sum.
 Single Bonds: F2
• Electron configuration of F: (1s)2(2s)2(2px)2(2py)2(2pz)1
• The VB wave function for the electron pair bond in F2 as

• This wave function gives no information on the eight pairs of electrons remaining
in their atomic orbitals on atoms A and B, six pairs of which are shown as
unshared pairs in the Lewis diagram for F2 (Fig. 6.28).
 Single Bonds: HF
• The VB model also describes bond formation in heteronuclear diatomic
molecules: HF
• One shared pair in a single bond produced by overlap of H 1s and F 2pz.

• The Pauli principle tells us that the spin part

of the wave function should be antisymmetric
(i.e. α(1)β(2) − α(2)β(1), where α indicates ms
= 1/2 and β indicates ms = − 1/2).
• σ bond: their electron density is cylindrically
symmetric about the bond axis.
• Each bond is formed by overlap of two AOs.
The electrons in the two participating AOs
must have opposite spin, so the bond
corresponds to an electron pair with opposite,
or paired spins.
 Multiple Bonds: N2
• Electron configuration of N: (1s)2(2s)2(2px)1(2py)1(2pz)1
• The two 2pz orbitals can overlap and form a σ bond whose wave function is

• The 2py orbitals (and the 2px orbitals) on the two atoms do not approach head-on
in this configuration: the 2py orbitals can overlap laterally. Together they form a π
bond, which has a node through the plane containing the bond axis with
amplitude above and below the plane.