MOLECULAR ORBITAL THEORY

Ref:
1. Miessler & Tarr, Inorganic Chemistry 4ed,2011, Pearson.
2. Silberberg, Chemistry: the molecular nature of matter and
change, 4Ed, Mc Graw Hill
3.Brady et al., Chemistry 5ed, 2009, Wiley
4.Zumdhal, Chemistry 6ed
 Schrodinger equation

• Constructed from Linear Combination of Atomic Orbital

• Sums and differences of atomic wave functions
= ca a + cb b

: molecular wave function

a : atomic wave functions for atom a and b
c : adjustable coefficients : can be equal/unequal,
positive/negative, depends on individual orbitals and
energies.
 Overlap of orbitals
• Covalent bonds are formed when atomic orbitals
overlap.
• two atoms are brought close together, distance
between 2 atoms decreased: molecular orbital form
• Electrons in MOs occupy space between nuclei,
strong electron attraction to both nuclei
(electrostatic forces)
 Essential conditions for overlap lead to
bonding
• 1. symmetry orbitals : same sign
2. similar energies
3. the distance between atoms must be short enough
 Molecular Orbital theory
• describes covalent bonds in terms of molecular
orbitals, which result from interaction of the atomic
orbitals of the bonding atoms and are associated
with the entire molecule.
• consider molecular orbitals as combinations of
atomic orbitals, specifically as linear combinations of
atomic orbitals (LCAO). The nuclei are bound
together by interaction with all of the electrons held
in the molecular orbital. All bonding is the result of
interactions between the valence electrons of atoms.
 The Central Themes of MO Theory

A molecule is viewed on a quantum mechanical level as a

collection of nuclei surrounded by delocalized molecular orbitals.

Atomic wave functions are summed to obtain molecular wave

functions.

If wave functions reinforce each other, a bonding MO is formed

(region of high electron density exists between the nuclei).

If wave functions cancel each other, an antibonding MO is formed

(a node of zero electron density occurs between the nuclei).
 Molecular Orbital Theory
• Waves that describe atomic orbitals have both positive
and negative phases or amplitudes.
• As MO’s are formed the phases can interact
constructively or destructively.

7
Figure 11.14
An analogy between light waves and atomic wave functions.

Amplitudes of wave
functions added

Amplitudes of
wave functions
subtracted.
 Constructive and Destructive Interference
• Additive combinations (constructive interference =
positive overlap) form bonding molecular orbitals
( , ).
– These are lower in energy than the atomic orbitals.
– The electrons in these orbitals spend most of their
time in the region in between the nuclei, helping to
bond the atoms together.
 Subtractive combinations
=destructive interference = negative overlap) form
antibonding molecular orbitals ( *, *).
– These are higher in energy than the atomic orbitals.
– The electrons in these orbitals can’t occupy the node
in the central region and don’t contribute to
bonding.
Figure 11.14 Contours and energies of the bonding and antibonding molecular
orbitals (MOs) in H2.

The bonding MO is lower in energy and the antibonding MO is higher in energy

than the AOs that combined to form them.
 *1s

• Decreased negative charge between nuclei

• Decreased attractions between negative
charge from electrons and positively charged
nuclei
• Higher potential energy than separate 1s
atomic orbitals
 1s

• Increased negative charge between nuclei

• Increased attractions between negative
charge from electrons and positively charged
nuclei
• Lower potential energy than separate 1s
atomic orbitals
• Same sign: + + or - - = positive overlap
= bonding orbital
different sign: + - = negative overlap
=antibonding orbital
 Diatomic(Molecules(
•  Consist(of(two(atoms:(
a)  Homonuclear(diatomic(molecules(–(iden8cal(
atoms((second(period(molecules(e.g.(Li2,(N2,(
O2)(
b)  Heteronuclear(molecules(–different(atoms(
(NO,(CN,(CO,(HF)(
Figure 11.16 The MO diagram for H2.

Filling molecular orbitals with electrons follows the

same concept as filling atomic orbitals.

*1s
Energy

1s 1s

H2 bond order
= 1/2(2 − 0) = 1
1s

AO MO AO
of H of H2 of H
 Bond order
• Lewis Structure: the number of electron pairs
shared by any pair of bonded atoms.
• MO Theory: the number of electrons in
bonding MOs minus the number in
antibonding Mos divided by 2.

Bond order= ½ [ no. e in bonding MO- no. e in antibonding MO]

 Bond order
• BO > 0 : molecular species is stable relative to
separate atoms
• BO=0 : no net stability, do not exist.
• 0<BO<1 : weak bond and exist
• The Higher the BO, the stronger the bond
 Bond%order%

bond%order%of%1%=%a%single%bond%
bond%order%of%2%=%double%bond%
bond%order%of%3%=%triple%bond%
%
½,%3/2%or%5/2%also%possible%
bond%order%of%0%=%no%bond%
%

1%
 Figure 11.17 MO diagram for He2+ and He2.

*1s *1s
Energy

Energy
1s 1s 1s 1s

1s 1s

AO of MO of AO of AO of MO of AO of
He He2+ He+ He He2 He

He2+ bond order = 1/2 He2 bond order = 0

 Figure 11.18 Bonding in s-block homonuclear diatomic molecules.

*2s
Energy

*2s

2s 2s 2s
2s

2s
2s

Li2 Be2

Li2 bond order = 1 Be2 bond order = 0

 Orbital states can be described with several
terms:
• Filled - An orbital that contains the maximum
number of electrons it can hold.
• Empty - An orbital that contains no electrons.
• Occupied - An orbital that contains at least
one electron.
• Unoccupied - An orbital that contains at least
one open space for an electron.
 Magnetism:

Paramagnetic:
• compounds that are weakly attractive in
magnetic fields,
• unpaired electrons
Diamagnetic:
• no unpaired electrons
• Not attracted to the magnetic field
 THE FRONTIER ORBITALS

Highest Occupied Molecular Orbital (HOMO)

• act as an electron donor,
• outermost (highest energy) orbital containing
electrons.
Lowest Unoccupied Molecular Orbital (LUMO).
• act as the electron acceptor,
• innermost (lowest energy) orbital that has room to
accept electrons.
• In accordance with the above definitions, a single
orbital may be both the LUMO and the HOMO.
Figure 11.19
Contours and energies of and MOs from
combinations of 2p atomic orbitals.
The molecular orbital diagram for a diatomic
O2 and F2
 F2

Bond Order = 1/2(10 - 8) = 1

stable.
diamagnetic.
electron configuration:
2 * 2 2 * 2 2 4 *2 4
1 1 2 2 2 2
 What%about%O2?%

Bond%order%=%
%
Stability%=%
%
Magne8c%behaviour%=%
%
MO%electron%configura8on%=%

1%
• Bond length : the distance between two
nuclei held together by a chemical bonding
• Bond Energy : the energy needed to break
one mole of a particular bond to give
electrically neutral fragment

• (Ref: Brady et al., Chemistry 5ed, 2009, Wiley)

 Why the bond energy is higher for O2
compare to F2?
• Bond lengths : O=O : 121pm
F-F : 142pm
• bond energies of O2 : 494 (kJ mol-1)
F2 : 155 (kJ mol-1)
The bond energy is higher for O=O than for F-F due to
• Bond order O2 =2, F2= 1
• O2: stronger bond – need more energy to break the
bond
• double O=O bond length is shorter than that of F-F.
 As a bond order increase

• bond strength increases

• the nuclei are pulled closer together
• which decreases the bond length
• bond energy increases.
 ORBITAL MIXING

• Orbitals of identical energies interact: no

orbital mixing
• Orbitals with similar (not equal) energies and
same symmetries interact: obital mixing
Variation of the energies of the 2s and 2p orbitals in
crossing the periodic table from Li to F
the separation between the ns and np
orbitals increases with increasing atomic
number.

Increasing atomic number, the effective nuclear charge

(and electronegativity) of the atoms increases. This is
why the energies of the analogous orbitals decrease
from Li2 to F2.
1. the separation between the ns and np orbitals
increases with increasing atomic number. Across the 2nd row
of the periodic table,
2s and 2p AOs (O, F & Ne) are so different in energy do
not interact with each other the orbitals do not mix

2. BUT B, C & N atoms are larger the 2p energies

are much closer to the 2s energy some mixing accurs
between the 2s orbital and the end-on 2p orbital of the
other atom sp mixing reverse in energy order of 2p
and 2p MOs
 Across the 2nd row of the periodic table, the amount of mixing (sp
mixing) decreases until there is no longer enough mixing to affect the
ordering; this happens at O2 (w/o or no sp mixing)
sp mixing : Li2 to N2
w/o sp mixing : O2 to Ne2
Molecular Orbital Energy-level
Diagram For The B2 Molecule.
When s-p mixing is allowed, the
energies of the 2p and π2p orbitals
are reversed. The two electrons
from the B 2p orbitals now occupy
separate, degenerate π2p
molecular orbitals and thus have
parallel spins. Therefore, this
diagram explains the observed
paramagnetism of B2.

Ref: Zumdhal, Chemistry 6ed

Figure 11.20 Relative MO energy levels for Period 2 homonuclear
diatomic molecules.
without 2s-2p with 2s-2p
mixing mixing

MO energy levels MO energy levels

for O2, F2, and Ne2 for B2, C2, and N2
MO#occupancy#
and#molecular#
proper0es#for#B2#
through#Ne2#

1"
SAMPLE'PROBLEM'11.4' Using'MO'Theory'to'Explain'Bond'Proper?es'

PROBLEM:' As#the#following#data#show,#removing#an#electron#from#N2#forms#an#
ion#with#a#weaker,#longer#bond#than#in#the#parent#molecules,#
whereas#the#ion#formed#from#O2#has#a#stronger,#shorter#bond:#
N2' N2+' O2' O2+'

Bond#energy#(kJ/mol)# 945# 841# 498# 623#

Bond#length#(pm)# 110# 112# 121# 112#

Explain#these#facts#with#diagrams#that#show#the#sequence#and#occupancy#of#MOs.#

PLAN:' Find#the#number#of#valence#electrons#for#each#species,#draw#the#MO#
diagrams,#calculate#bond#orders,#and#then#compare#the#results.#

SOLUTION:'

N2#has#10#valence#electrons,#so#N2+#has#9.#

O2#has#12#valence#electrons,#so#O2+#has#11.#

1#
 Zero overlap
• AOs do not interact/overlap
• Not involved in bonding
• Called nonbonding molecular orbital
 Heteronuclear diatomic molecules

• Molecules Composed of two different atoms

• Different electronegativity
• eg: NO , CN , CO, HF
Heteronuclear+Diatomic+Molecules++

•  Molecular+orbital+diagrams+for+heteronuclear+
molecules+have+skewed+energies+for+the+
combining+atomic+orbitals+to+take+into+account+
the+differing+electronega:vi:es.++

•  T︎ he+more+electronega:ve+elements+are+lower+
in+energy+than+those+of+the+less+
electronega:ve+element.++
 Heteronuclear+Diatomic+Molecules++
•  The+energy+differences+between+bonding+orbitals+
depend+on+the+electronega:vity+differences+
between+the+two+atoms.+

–  The+larger+the+difference+the+more+polar+the+bond+
that+is+formed+(ionic+character+increases).+
+
–  The+difference+reflects+the+amount+of+overlap+
between+the+bonding+orbitals.+If+the+difference+is+too+
great+the+orbitals+cannot+overlap+effec:vely+and+
nonbonding+orbitals+will+be+formed.++
+ Orbital interactions that produce bonding or antibonding orbitals in heteronuclear
diatomics occur if there is sufficient overlap between atomic orbitals, as determined by
+ their symmetries and similarity in orbital energies.
While MOs for homonuclear diatomic molecules contain equal contributions from each interacting
atomic orbital, MOs for heteronuclear diatomics contain different atomic orbital contributions.
Relative energies of interacting orbitals must be similar

Strong interaction Weak interaction

The more electronegative (or higher nuclear charge) element's

orbitals are placed lower on the correlation diagram than those
of the more electropositive element
Similar electronegativity : NO

OR
In heteronuclear diatomic molecules, atomic
orbitals only mix when the electronegativity values
are similar. In carbon monoxide (CO), the oxygen
2s orbital is much lower in energy than the carbon
2s orbital, so the degree of mixing is low
 HF
• Fluorine is more
electronegative than hydrogen
– the atomic orbital energies are
very different
– the 1s orbital on H and the 2p
orbital on F combine to form a
molecular orbital.
– the electron density is not
equally distributed .
– greater electron density around
the fluorine atom
 HF

In hydrogen fluoride, HF, symmetry allows for overlap between the H 1s and F 2s orbitals, but the
difference in energy between the two atomic orbitals prevents them from interacting to create a
molecular orbital.

Symmetry also allows for overlap between the H 1s and F 2pz orbitals, and these two atomic orbitals
have a small energy separation; they therefore interact, creating σ and σ* MOs and a molecule with a
bond order of one. 45
 HF

• Very polar bond because the electronegativity

difference between H (EN=2.2) and F (EN=4.0) is very
large ( EN=1.8)
• Overlap 1s(H) with 2p(F) = sp and *sp
• Remaining two 2p(F) = no net overlap with H
orbital = nonbonding orbital (same as 1s and
2s of F)
• Nonbonding orbitals retain the characteristic
of F AOs from which they are formed.
 Non-bonding electrons
*

1s

2p 2p

H F
2s 2s

Bond order:
(2 – 0)/2 = 1

1s 1s
48
• The closer in energy a MO is to
the energy of one of the AO of
which is composed, the more of
the character of that AO it
show.
– The bonding ( sp ) MO more
Fluorine-like character
– The antibonding ( sp *) MO
has more hydrogen-like
character