HOW ARE THE

OBSERVED BOND ANGLES ACHIEVED?

HYBRIDIZATION

“Vision is the art of seeing things invisible.”

Jonathan Swift
WHY DOESN’T THE ATOMIC ORBITAL APPROACH WORK ?

These orbitals are for the During bonding …. After bonding (overlap)
atom - we can’t expect new orbitals form that we get a totally
that they are suitable for are more suitable for new solution for the
the molecule. making bonds. new molecule.

2s sp,sp
2px,2py,2pz 2py,2pz σ, π, π ,n

atomic hybrid atomic molecular

orbitals orbitals orbitals
LCAO overlap

HYPOTHETICAL BONDING PROCESS

NOTE. Formally LCAO theory and Molecular Orbital theory are

two completely different approaches. You do not need to use
hybid orbitals to derive the molecular orbitals, combinations
of any type of function will do. Nevertheless, the abstraction
presented above is quite useful, as we will see quite soon.
 HYBRID ORBITALS
PRECURSORS TO THE FINAL RESULT

We will concentrate first on hybrid orbitals.

ADVANTAGE
HYBRID ORBITALS allow us to correctly
predict the final shape of the molecule.

DISADVANTAGE
Hybrid orbitals are an abstraction and are
not the final MOLECULAR ORBITALS that
result after bonds form.

The types of hybrids common to organic

molecules follow ……
 sp 3

TETRAHEDRAL HYBRIDIZATION

4 pair in the valence shell

(no double or triple bonds)
 FORMATION OF TETRAHEDRAL HYBRID ORBITALS
New orbitals point
to the corners of a 4 pair
tetrahedron.
sp3(1)

2p
109o28’ FILLED VALENCE
2s SHELL

O
hybridization
sp3(3) occurs when orbitals
are full and have
finished bonding

sp3(4)
sp3(2) (1) (2) (3) (4)
tetrahedral geometry sp3 hybrid orbitals
(cartoon)
FORMATION OF
SP3 HYBRID ORBITALS 2p
(1) (2) (3) (4)
2pz
2s

2s

X 2px

2py
sp3 hybridized
unhybridized
atom
These orbital shapes are
cartoons - actual shapes
are shown on the next
slide. [animation]
 SP3 HYBRID ORBITAL
( cross section )
sp3
… and its cartoon
The hybrid orbital
has more density
in the bonding lobe
than a p orbital and
forms stronger bonds.

To avoid confusion the The shape shown

back lobe is omitted is calculated from
from the cartoons, quantum theory.
already shown, and the Courtesy of
front lobe is elongated Professor George Gerhold
to show its direction.

omitted
 ORIGIN OF THE SP3 DESIGNATION

add together, divide in four

hybridization

2s 2p

(1) (2) (3) (4)

sp3 hybrid orbitals
each new orbital is
1/4 s + 3/4 p (25% s, 75% p)

S1P3 = SP3
( 1+3 ) = 4 parts total
ORIGIN OF THE SP3 ORBITAL SHAPE
2s orbital
sp3 hybrid
orbital

2p orbital

+
x
-- ++

RECALL:
signs are mathematical
coordinates, not
electronic charge
[animation]
HYBRIDIZATION
 sp 2

TRIGONAL PLANAR HYBRIDIZATION

3 pair in the valence shell

and either an incomplete
octet or a double bond
FORMATION OF TRIGONAL PLANAR HYBRID ORBITALS

unused 2p
3 pair unused
orbital
sp2(2)
2p 2p
3 orbitals
2s filled

B x hybridization

120o
sp2(1)
2p

trigonal sp2(3) (1) (2) (3)

planar sp2 hybrid orbitals
z
 SP2 HYBRID ORBITAL
cusp
more density in
the bonding lobe
sp2 than in an sp3
orbital

smaller tail
than in an
sp3 orbital
Courtesy of
Professor George Gerhold
 sp

LINEAR HYBRIDIZATION
 FORMATION OF LINEAR HYBRID ORBITALS

unused 2p
2 pair unused
orbitals

2p 2p
y
2 orbitals
sp(1) 2s filled

C x hybridization

sp(2)
2p
(1) (2)
linear sp hybrid orbitals
z
 SP HYBRID ORBITAL

more density in
the bonding lobe
sp than in an sp2
orbital

smaller tail
than in an
sp2 orbital
Courtesy of
Professor George Gerhold
COMPARISON OF THE HYBRIDS
COMPARISON OF SPx HYBRID ORBITALS
bigger
“cusp”
“tail”
more “p” character

sp3 sp2 sp

more “s” character

more electron
Orbital plots courtesy of density in the
Professor George Gerhold bonding lobe
 more
sp3 p-like

HYBRID ORBITALS
COMPARISONS OF
sp2 BONDING DISTANCE
SIZE OF CUSP
SIZE OF TAIL

sp more
s-like Orbital plots courtesy of
Professor George Gerhold

makes shorter, stronger bonds

WHY DO HYBRIDS FORM ?
 WHY DO HYBRIDS FORM?

1. Electron pair repulsions are minimized (= lower energy)

2. Stronger bonds (= lower energy) are formed

3. Hybrids have better directionality for forming bonds

4. Since promotion usually occurs, hybrids allow

more bonds to form (= lower energy)
CONSTRUCTION BLOCKS

THE HYBRIDS ARE “MOLECULAR LEGOS”

EACH IS USED IN A SPECIFIC BONDING SITUATION
 HYBRID CONSTRUCTION BLOCKS

4 PAIR 3 PAIR 2 PAIR

TETRAHEDRAL TRIGONAL LINEAR
PLANAR
sp3 sp2 sp

X Y Z

109o28’ 120o 180o

X
Y
X Z
Y
Z
X Y
Z
Y
 SIGMA BONDS

BOND LENGTHS AND STRENGTHS

Shorter = Stronger = (more) S-character

BOND LENGTHS AND OVERLAP
Overlap leads to the bond.

In general, the more overlap that

can be established, the stronger
the bond that is formed.

sp3
Orbitals that
have more
Shorter bonds s-character
establish more place more (%)
overlap and are electron density
stronger bonds. in the bonding
lobe and form
stronger bonds.
sp
BOND STRENGTHS - C-H SINGLE BONDS
C-H bond energy molecule
bond type length per mole measured

Kcal ( KJ )
unhybridized
[CH2] 2p-1s 1.12 A 80 (335) intermediate

C-H sp3-1s 1.10 A 101 (422) CH3CH3

C-H sp2-1s 1.08 A 106 (444) CH2=CH2

C-H sp-1s 1.06 A 121 (506) =

HC=CH
increasing
s-character

NOTE: more S = Shorter = Stronger

Hybridization makes stronger bonds.
BOND STRENGTHS - C-C SINGLE BONDS
C-C bond energy molecule
bond type length per mole measured

Kcal ( KJ )

-C-C- sp3-sp3 1.54 A 83 (347) CH3-CH3

-C-C= sp3-sp2 1.51 A 109 (456) CH3-CH=CH2

=
-C-C= sp3-sp 1.46 A - - CH3-CH=CH2

increasing
s-character Typical sigma bonds have energies
in the range 80-120 kcal/mole
DIFFERENCES BETWEEN
SIGMA AND PI BONDS
 PI (π) BONDS
In a multiple bond, the first bond is a sigma σ bond
and the second and third bonds are pi π bonds.

π π
π

C C C C

σ σ

Pi bonds are formed differently than sigma bonds.

SYMMETRY DIFFERENCES IN SIGMA AND PI BONDS
SIGMA BONDS
symmetric to
rotation about
internuclear
axis
σ 1s-2p

END-TO-END
OVERLAP σ 2p-2p

PI BONDS
not symmetric

SIDE-TO-SIDE
OVERLAP
π 2p-2p
ONLY ONE SIGMA BOND CAN FORM
You can’t form more than one sigma bond along the
internuclear axis.

When you try to form more than

one sigma bond, you get bent bonds.
X

Bent bonds are not

as strong as pi bonds.
TYPES OF ELECTRONS IN A MOLECULE

SYMBOLS FOR
BONDED ELECTRONS AND
NON-BONDED ELECTRONS
 STANDARD SYMBOLS

Types of Bonds: σ and π

.. n
O :
σ π
H3C CH3

Non-Bonded Pairs : n
 PI BONDS

BOND LENGTHS
AND STRENGTHS

PI BONDS ARE WEAKER THAN SIGMA BONDS

BOND STRENGTHS - MULTIPLE BONDS

CC bond bond bond energy molecule

bond type length per mole measured

Kcal (KJ)

C-C sp3-sp3 1.54 A 83 (347) CH3CH3

C=C sp2-sp2 1.34 A 146 (611) CH2=CH2

=
C=C sp - sp 1.20 A 200 (837) =
HC=CH
shorter
increasing Typical pi bonds have a bond
s-character energy of about 50-60 kcal/mole

The shorter sigma bond that

results is also stronger.
A TABLE OF BOND ENERGIES
FOR REFERENCE
 H C N O F Si S Cl Br I

H 104 99 93 111 135 76 83 103 87 71 H

C 83 73 86 116 72 65 81 68 52 C

N 39 53 65 - - 46 - - N

O 47 45 108 - 52 48 56 O

F 37 135 - - - - F

Si 53 - 91 74 56 Si
AVERAGE BOND
S 60 61 52 - S
ENERGIES FOR
SINGLE BONDS
Cl 58 - - Cl
( Kcal / mole )
Br 46 - Br

I 36 I