Chapter 5

Molecular Orbitals (MO)

◆ Molecular orbital (MO) theory uses group theory

to describe the bonding in molecules
◆ Molecular orbitals are formed by the combination
of atomic orbitals
◆ The symmetry properties and relative energies of
atomic orbitals determine how these orbitals interact
to form molecular orbitals
◆ We describe the pictorial approach and develop
the symmetry methodology required for complex
cases
Contents
 Characteristics
of Molecular Orbitals

• Two atomic orbitals combine => two molecular

orbitals result.
• Of each pair of molecular orbitals, one is a bonding
molecular orbital.
– The bonding orbital is at a lower energy than the separate
atomic orbitals.
– Electrons in a bonding orbital increase the stability of the
molecule.
• The second orbital is an antibonding orbital.
– The antibonding orbital is at a higher energy than the AOs.
– Electrons in an antibonding orbital decrease the stability of
the molecule.
 Types of Molecular Orbitals

Electron density … an antibonding

between the nuclei is molecular orbital,
decreased. higher in energy
than the AOs.

s1s* = c2 [Y1sa - Y1sb]

a b … a bonding
molecular orbital,
lower in energy
than the AOs
Electron density
Two AOs in between the nuclei
hydrogen atoms is increased.
combine to form …

s1s = c1 [Y1sa + Y1sb]

Molecular Orbitals from Atomic Orbitals
Approximate solutions to these molecular Schrodinger equations can
be constructed from linear combinations of atomic orbitals
(LCAO), the sums and differences of the atomic wave functions.

Y is the molecular wave function, Ya and Yb are atomic wave

functions for atoms a and b, and ca and cb are adjustable coefficients

Three conditions are essential for overlap to lead to bonding

1.The symmetry of the orbitals must be such that regions with
the same sign of Y overlap.
2.The atomic orbital energies must be similar.
3.The distance between the atoms must be short enough to
provide good overlap of the orbitals, but not so short that
repulsive forces of other electrons or the nuclei interfere.
 MOs from Hydrogen 1s Orbitals
An asterisk is used to
indicate antibonding orbitals
 Nonbonding Orbitals

The energy of a
nonbonding orbital
is essentially that of
an atomic orbital,
either because the
orbital on one atom
has a symmetry that
does not match any
orbitals on the other
atom or the orbital
on one atom has a Nonbonding
severe energy MO
mismatch with
symmetry-
compatible orbitals Nonbonding
on the other atom. MO
 MOs for the 2p Electrons

The two px
orbitals combine
to form sigma
bonding and
antibonding MOs.

The two py orbitals

and the two pz
orbitals give pi
bonding and
antibonding MOs.
 Formation
of MOs Orbitals that do
not form MOs

Energy
Level
Diagram

Interactions
of
p Orbitals
 Overlap Regions
of the Combination of Orbitals

all with collinear z axes

z
 Interactions of d Orbitals

(a) Formation of molecular orbitals. (b) Atomic orbital combinations

that do not form molecular orbitals.
 MOs from d Orbitals
1 strong
s interaction

Inter-nuclear axis: z

2 medium
p interactions

2 weak
d interactions
 Relative Energies of Orbitals from d-Orbital Interactions

M-L s*
Re2Cl82-

5 bonding
MO in the Small separation D4h: two Re-Cl (xz & yz planes)
absence of visible range: colorful Re-Re (z axis),
ligands
the eclipsed configuration is
required to form the d bond!

dxy

dxz dyz
Used in the M-L
s bond (No M-M bond)
dz2

Chapter 13
MOs for the first 10 Elements

Assuming Significant
Interactions Only
between the Valence
Atomic Orbitals of
Identical Energy
 Homonuclear Diatomic Molecules (2nd Period)

Energy
levels
should be
confirmed
Bond length (Å ) 2.67 - 1.59 1.24 1.10 1.21 1.42 - by
Bond energy (kJ) 110 - 272 602 941 493 138 - experiment!
Bond order 1 0 1 2 3 2 1 0
 Importance of Experimental Evidence

• The Lewis structure

commonly drawn for oxygen
is

• But oxygen is paramagnetic,

and therefore must have
unpaired electrons.

• Lewis structures are a useful

tool, but they do not always
represent molecules correctly,
even when the Lewis
structure is plausible.
Need to turn to quantum mechanical approach to chemical bonding!
 Magnetic Properties

• Diamagnetism is the weak repulsion associated

with paired electrons.
• Paramagnetism is the attraction associated with
unpaired electrons.
– This produces a much stronger effect than the
weak diamagnetism of paired electrons.
• Ferromagnetism is the exceptionally strong
attractions of a magnetic field for iron and a few
other substances.
 Orbital Mixing

• Molecular orbitals with similar energies interact if they have appropriate

symmetry
• When two MOs of the same symmetry mix, the one with higher energy
moves still higher in energy, and the one with lower energy moves lower.
Mixing results in additional electron stabilization, and enhances the bonding.
 Energy Levels of
Homonuclear Diatomic Molecules (2nd Period)

Orbital Mixing

Energy
- C2 is a rarely encountered allotrope of carbon.
- The acetylide ion, C22-, is well known, particularly
in compounds with alkali metals, alkaline earths,
and lanthanides. According to the molecular
orbital model, C22- should have a bond order of 3.

- The energy-level shift caused by s-p mixing is vital to

understand the bonding in N2. In the absence of
mixing, the sg(2p) orbital would be expected to be
lower in energy than the pu(2p) orbitals.
? - Mixing of the sg(2s) orbital with the sg(2p) orbital
lowers the energy of the sg(2s) orbital and increases
the energy of the sg(2p) orbital to a higher level than
the p orbitals.
- The sg(2p) and pu(2p) levels are very close in energy.
The order of energies of these orbitals has been
controversial.
- The extent of s-p mixing is not sufficient in O2 to push the
sg(2p) orbital to higher energy than the pu(2p) orbitals. The order
of molecular orbitals shown is consistent with the photoelectron
spectrum.
- Oxygen–oxygen distances in O2- and O22- are influenced by the
cation.
Bond Lengths in
Homonuclear
Diatomic
Molecules

The increasing
nuclear charge pulls
the electrons closer to
the nucleus
 Photoelectron Spectroscopy
- The quantitative information
regarding the electronic structure
and bonding can be determined
from photoelectron spectroscopy. the highest
- Ultraviolet light (UPS) or X-rays occupied orbitals
(XPS) eject electrons from of the N2+ ions.
molecules: N2 + hn(photons) 
N2+ + e-
- The kinetic energy of the expelled
electrons can be measured;
Ionization energy = hn(energy of
photons) - kinetic energy of the
expelled electron
- If the energy levels of the ionized
molecule are assumed to be
essentially the same as those of
the uncharged molecule, the
observed energies can be
directly correlated with the MO
energies.
 X-ray Photoelectron Spectroscopy
(XPS)

- also known as ESCA, an abbreviation for electron spectroscopy for chemical

analysis
- XPS detects all elements with an atomic number (Z) of 3 (lithium) and above.
It cannot detect hydrogen (Z = 1) or helium (Z = 2) because the diameter of
these orbitals is so small, reducing the catch probability to almost zero.
 Orbitals that are strongly
involved in bonding have
multiple peaks; orbitals that
are less involved in bonding
have only a few peaks at
each energy level This orbital is less involved in
bonding (removing electron
does not change bond strength)

They are more

involved in the bonding
than either of the s
orbitals.
 The spectrum provides evidence of
the quantized electronic and
Energy Levels of vibrational energy levels of the
N2 & O2 molecule

N2 O2
 Vibronic Coupling
“Vibronic" originates from the combination of the terms "vibrational" and
"electronic". Vibrational and electronic interactions are interrelated and the
magnitude of vibronic coupling reflects the degree of such interrelation.

energy

υ5’ coupled vibration

υ3’ υ4’
υ1’
electronic excited
state is ‘g’

g→(g+u) transition
is allowed
υ5 g→g transition
υ3 is forbidden The band one sees in the UV-visible
υ1 spectrum is the sum of bands due to
electronic ground transitions to coupled electronic (E) and
state is ‘g’ vibrational energy levels (υ1, υ2, υ3)
 Heteronuclear Diatomic Molecules
The application of MO theory to heteronuclear diatomic molecules is similar
to its application to homonuclear diatomics, but the different nuclear charges
of the atoms require that interactions occur between orbitals of unequal
energies and shifts the resulting molecular orbital energies.

-13

attraction between
valence electrons and
atomic nuclei.

 nucleus charge 
 The atomic orbital closer in
energy to an MO contributes more
to the MO, and its coefficient is
larger in the wave equation.

Mixing of the s and s* levels

This is the result of significant causes a larger split in energy
interactions between the 2pz orbital of O between the 2 s* and 3s, and the
and both the 2s and 2pz orbitals of C. 3s is higher than the 1p levels.

2s 2p
C
N
O
Molecular Orbitals
and
Photoelectron
Spectrum of CO
 lowest unoccupied
molecular orbital

Molecular Orbitals
of CO

highest occupied
molecular orbital

The shape of the 3s orbital is a very large lobe on the carbon end. This
is a consequence of the ability of both the 2s and 2pz orbitals of
carbon to interact with the 2pz orbital of oxygen; the orbital has
significant contributions from two orbitals on C but only one on O,
leading to a larger lobe on the C end.
 Metal Carbonyl Complexes

The electrons of the HOMO are of highest

energy; these are generally the most
energetically accessible for reactions with
empty orbitals of other reactants. The LUMOs
are the 1p* orbitals; like the HOMO, these are
concentrated on the less electronegative C,
a feature that also predisposes CO to
coordinate to metals via the C atom. The
frontier orbitals can both donate electrons
HOMO (HOMO) and accept electrons (LUMO) in
reactions.

Covalent (M-CO) versus

Ionic (M-OC) Bonds
 Polar Bond (HF)

Nonbonding:
fluorine 2px and
2py orbitals

1 bonding pair and 3 lone pairs;

the lone pairs are not equivalent
 Ionic Compounds and Molecular Orbitals
- Ionic compounds can be considered the limiting form of polarity.
- At the limit, the electron is transferred completely to the more
electronegative atom to form a negative ion, leaving a positive ion with a
high energy vacant orbital. (Ionic Bond!)
- In molecular orbital terms, we can treat an ion pair like we do a covalent
compound. (Band Theory for Extended Solid!)

LiF exists as a crystalline solid; this

form of LiF has significantly lower
energy than diatomic LiF. Ionic
salts do not exhibit directional
bonds, in contrast to molecules
with highly covalent bonds
Molecular Orbitals for Larger Molecules

- Group orbitals, collections of matching orbitals on

outer atoms (or ligands). Metal-Ligand concept.
- To generate a set of group orbitals, we will use the
valence orbitals of the outer atoms. We will then
examine which central-atom orbitals have the proper
symmetry to interact with the group orbitals.

Process Used in Creating Molecular Orbitals

3. Construct a (reducible) representation for the combination of
the valence s orbitals on the outer atoms. If the outer atom is not
hydrogen, repeat the process, finding the representations for each
of the other sets of outer atom orbitals (for example, px, py, and
pz).
4. Reduce each representation from Step 3 to its irreducible
representations. This is equivalent to finding the symmetry of the
group orbitals or the symmetry-adapted linear combinations
(SALCs) of the orbitals. The group orbitals are then the
combinations of atomic orbitals that match the symmetry of the
irreducible representations.

5. Identify the atomic orbitals of the central atom with the same
symmetries (irreducible representations) as those found in Step 4.

6. Combine the atomic orbitals of the central atom and those of

the group orbitals with matching symmetry and similar energy
to form molecular orbitals. The total number of molecular
orbitals formed must equal the number of atomic orbitals
used from all the atoms.
 Molecular Orbitals of CO2 (ML2)

3. Reducible Representations for Outer Atom Orbitals:

In CO2 these are the 2s and 2p oxygen orbitals. These can
be grouped into four sets.
4. Group Orbitals from Reducible Representations: Each of the
representations from Step 3 can be reduced by the procedure
described in Section 4.4.2. For example, the representation (2s)
reduces to Ag + B1u:

2s reduces to Ag + B1u
2pz reduces to Ag + B1u
2px reduces to B2g + B3u
2py reduces to B3g + B2u
 Oxygen
orbital used
5. Matching Orbitals on the Central Atom: To determine which
atomic orbitals of C are of correct symmetry to interact with the
group orbitals, we will consider each group orbital separately. The
carbon atomic orbitals are with their symmetry labels within the
D2h point group.
 6. Formation of Molecular Orbitals: Group orbitals 1 and 2, formed
by adding and subtracting the oxygen 2s orbitals, have Ag and B1u
symmetry, respectively. Group orbital 1 is of appropriate symmetry to
interact with the 2s orbital of carbon (both have Ag symmetry), and
group orbital 2 is of appropriate symmetry to interact with the 2pz
orbital of carbon (both have B1u symmetry).

Group Group
Orbital 1 Orbital 2
Ag B1u
Group
Orbital 3
Ag

B1u

Group
Orbital 4
 B3g
B2u Group
Orbital 6

Group
Orbital 5

there is no carbon orbital with

B3g symmetry to interact with
group orbital 6. Group orbital 6
is nonbonding

B2g Group orbital 8 is nonbonding

Group
B3u Orbital 8

Group
Orbital 7
Molecular 16 valence electrons occupy 2
Orbitals of essentially nonbonding s
orbitals, 2 bonding s orbitals,
CO2 2 bonding p orbitals, and 2
nonbonding p orbitals. In other
words, two of the bonding
electron pairs are in s orbitals,
two are in p orbitals, and there
are four bonds in the molecule.
B1u, B2u, B3u

Ag, B1u, Ag, B1u, B2g, B3u, B3g, B2u

Ag
8 GO + 4 AO
= 12 MO

Ag, B1u

1s22s22p2 1s22s22p4
 Molecular Orbitals of H2O
1. Water is a bent molecule with a C2 axis through the oxygen and two
mirror planes that intersect along this axis. The point group is C2v.
2. The C2 axis is chosen as the z axis and the xz plane as the plane of
the molecule. Because the hydrogen 1s orbitals have no directionality,
it is not necessary to assign axes to the hydrogen atoms.
3. The hydrogen atoms determine the symmetry of the molecule, and
their 1s orbitals form the basis of a reducible representation.
4. The representation G can be reduced to the irreducible
representations A1 + B1, representing the symmetries of the
group orbitals. In Step 5 these group orbitals will be matched with
oxygen orbitals of matching symmetries.
5. The first step in deducing the molecular orbitals is to combine
the two hydrogen 1s orbitals to afford group orbitals.

A1 = B1 =
6. The atomic and group orbitals with the same symmetry are
combined into molecular orbitals. They are numbered 1 through 6
in order of their energy, with 1 the lowest and 6 the highest.

Group Orbitals (H) Atomic Orbitals (O) Molecular

A1, B1 + A1, A1, B1, B2 Orbitals

The A1 group orbital combines with the s and pz orbitals of the oxygen to
form three MOs (Y1, Y3, Y5).

The B1 group orbital combines with the oxygen px orbital to form two
MOs (Y2, Y6). The oxygen py (Y4, with B2 symmetry) is non-bonding.
Two bonding orbitals (Y2, Y3),
one nonbonding (Y4), one
essentially nonbonding orbital
Y1, and two antibonding
orbitals (Y5, Y6)

2 GO + 4 AO A1, B1
= 6 MO

When the 8 valence electrons A1, B1, B2

are added, 2 pairs occupy
bonding orbitals, and 2 pairs
occupy nonbonding orbitals;
this complements the 2 bonds
and 2 lone pairs of the Lewis
electron-dot structure.

A1
 Molecular Orbitals of NH3
Deducing group orbitals is no longer possible with NH3.
The projection operator method, a systematic approach
for deduction of group orbitals, is the preferred strategy.
 Projection Operators to Deduce SALCs
The projection operator method permits elucidation of how atomic orbitals
should be combined to afford the symmetry-adapted linear
combinations (SALCs) that define the group orbitals.
SALC(A1) =

SALC(E) =

How can you get the second SALC(E)?

Projection Operators
 - derive the SALCs formed by the H 1s orbitals in NH3
- SALCs span irreducible representations A1 + E
- effects of the symmetry operations on the basis functions
h1, h2 and h3

h3 + h2
A1

the same
normalized form
A2

The projected function is zero in each case, as

expected because the A2 irreducible representation
is not covered by the basis of 3 H1s functions.

They are not orthogonal to each other. E is a doubly degenerate

representation. This is a problem with projection operators. The
Schmidt orthogonalization procedure can extract SALCs from a non-
orthogonal linear combination of an appropriate basis.

two orthogonal
p orbitals
Normalization of SALCs
Orthogonalization
From Group
Properties
The nitrogen s and pz orbitals
combine with the hydrogen A1
group orbital to give three a1
orbitals: 1 bonding, 1
nonbonding orbital, and 1
antibonding orbitals

The nitrogen px and py orbitals

combine with the E group
A1, E1
orbitals to form four e orbitals, A1, E1

2 bonding and 2 antibonding.

When the 8 valence electrons
are added, 3 pairs occupy
bonding orbitals, and 1 pairs
occupy nonbonding orbitals

HOMO: slightly
bonding, because it
A1
contains an electron
pair in an orbital
N=1s2 2s22p3
Molecular Orbitals of NH3
Molecular Orbital Theory
 CO2: Revisited with Projection Operators
The orbitals previously was deduced by matching their
symmetries to the corresponding irreducible representations,
a complementary strategy is to employ projection operators.

A1 group orbital was used as the basis

2s group orbital possess Ag and B1u symmetry

Normalization results in
the expected group orbitals (SALCs)
2pz group orbital also possess Ag and
B1u symmetry

2pz reduces to Ag + B1u

SALCs for the 2px orbitals exhibit B3u
and B2g symmetries

2px reduces to B2g + B3u

SALCs for the 2py orbitals exhibit B2u
and B3g symmetries

2py reduces to B3g + B2u

Molecular 16 valence electrons occupy 2
essentially nonbonding s
Orbitals of orbitals, 2 bonding s orbitals,
CO2 2 bonding p orbitals, and 2
nonbonding p orbitals. In other
words, two of the bonding
electron pairs are in s orbitals,
two are in p orbitals, and there
are four bonds in the molecule.

B1u, B2u, B3u

Ag, B1u, Ag, B1u, B2g, B3u, B3g, B2u

Ag
8 GO + 4 AO
= 12 MO

Ag, B1u

1s22s22p2 1s22s22p4
 Hybrid Orbitals
- Modern inorganic literature almost exclusively
employs molecular orbital theory to gain insights
regarding structure and bonding.
- The hydridization model when it is convenient to help
visualize an interaction. In the hybrid concept, the
orbitals of the central atom are combined into sets of
equivalent hybrids. The hybrid model is especially
useful in organic chemistry (sp3)
- Hybrid orbitals are localized in space and are
directional, pointing in a specific direction.
- The symmetry properties of a set of hybrid orbitals will
be identical to the properties of a set of vectors with
origins at the nucleus of the central atom and pointing
toward the surrounding atoms.
The sp3 Hybridization Scheme

Four AOs form four new hybrid AOs

 Hybrid Orbitals: CH4

Bond Vectors
In Methane

◈ The atomic orbitals of carbon used in the hybrids

must have symmetry matching A1 + T2; more specifically,
one orbital must match A1, and a set of three
(degenerate) orbitals must match T2 .

◈ A1 has the same symmetry as the 2s orbital of carbon;

T2 has the same symmetry as the three 2p orbitals or the
dxy, dxz, and dyz orbitals taken together.
 Molecular Orbitals of CH4

C=1s2 2s22p2
 Hybrid Orbitals: CH4

Bond Vectors
In Methane

◈ The atomic orbitals of carbon used in the hybrids

must have symmetry matching A1 + T2; more specifically,
one orbital must match A1, and a set of three
(degenerate) orbitals must match T2 .

◈ A1 has the same symmetry as the 2s orbital of carbon;

T2 has the same symmetry as the three 2p orbitals or the
dxy, dxz, and dyz orbitals taken together.
Molecular Orbitals of CH4
excited-state
◈ The s orbital is not listed, but understood to be present for the
totally symmetric representation.
◈ The functions listed for E’ symmetry match the px, py set.
MOs for Octahedral Metal Complexes
Consider only six s ligand donor orbitals (z axis)!

G (s) = A1g + T1u + Eg

Possible combination
4s + (4px, 4py, 4pz) + (3dx2-y2, 3dz2)
sp3d2

See p 111-115
Reducible to Irreducible Representation

1
ai   g (c)  red (c) *  (l ) (c)
(l )

h l
Order
C3 v E 2C3 3s v
Gred 4 1 2
a A1  1 4 1  2 11  3  2 1  2
1
A1 1 1 1
6 A2 1 1 1

a A2  1 4 1  2 11  3  2 1  0

1 E 2 1 0

6
aE  1 4  2  2 11  3  2  0   1
1
6
Gred = 2A1 + E
Sigma-Donor Interactions with Metal d Orbitals

dx2-y2, dz2

Non-bonding
interaction
 A1g, Eg, and T1u Stretching Modes of
an ML6 Complex

g (gerade):
symmetric to inversion
u (ungerade):
antisymmetric to inversion

(A1g: 4s), (T1u: 4px, 4py, 4pz),

(Eg: 3dx2-y2, 3dz2)
See p 107
Projection Operators
+
Schmidt
Orthogonalization
Symmetry Labels for Configurations

-1 -2

2 1 0

E A T
 MOs for an Octahedral
6 antibonding orbitals
Metal Complex
with a1g, t1u, eg

Calculated for green

[Ni(H2O)6]2+ Bonding MO,
No~op!

only s bonding, no p bonding

Metal T2g orbitals do not have
appropriate symmetry to
interact with the ligands. So, T2g
orbitals are nonbonding

6 bonding orbitals (a1g, t1u, eg) filled by

electrons donated by the ligands G (s) = A1g + T1u + Eg

6 LO + 9 AO
= 15 MO
Coordinate System for Octahedral p Orbitals

G (ps) = A1g + T1u + Eg

G (ss) = A1g + T1u + Eg

M

6 s orbitals, 6 py orbitals, 12 px & pz orbitals, 9

orbitals from metal = 33 orbitals form a basis set

A set of 12 vectors representing the p bonds, which form a basis

 Sigma-Donor and Pi-Acceptor Interactions
with Metal d Orbitals

t2g matches the dxy,

dyz, dxz orbitals
available for p bonds
distributed over the 6 18 LO + 9 AO
M-L pairs = 27 MO

form bonding
molecular orbitals
 t2g matches the dxy, dyz, dxz orbitals available
Effect of p for p bonds distributed over the 6 M-L pairs
Bonding on D0
(d3 Ions)
Calculated for
colorless Cr(CO)6

p back-bonding, with
electrons from the metal
d orbitals donated back
to the ligands

Non-bonding in
the s only orbital
calculation
p acceptor
CN-, CO
L M : s donation
M  L : p donation F-, Cl-
more negative charge
on M due to p & s donations
 Homework
제출: 일주일 후 강의 시작 전!! Group Study 통해 문제 풀 경우 반드시 참여자 명시!