10.

Chemical Bonding II: Molecular Geometry

and Hybridization of Atomic Orbitals

molecular shape
most molecules are 3-D objects
bond lengths and bond angles
Lewis structures convey no 3-D information
Valence Shell Electron Pair Repulsion model: VSEPR (vesper)
electron pairs repel each other = electron pairs tend to remain
as far apart as possible
lone pair lone pair lone pair bond pair > bond pair bond
pair
electrons are anchored to central atom, lie on a sphere: valence
shell

two pairs W 180 linear

three pairs W 120 trigonal planar

four pairs W 109.5 tetrahedral

GChem I

10.1

electron-pair geometry
does not have to be equal to
molecular geometry

molecular geometry = geometry of the atomic nuclei bound to

the central atom: bond pairs
VSEPR notation: A = central atom, B = atom bonded to central
atom, E = lone pair on the central atom
Exercise: Determine the shape of PF5
procedure: (1) obtain Lewis structure; (2) write down VSEPR
notation; (3) determine electron-pair geometry; (4) determine
molecular geometry
(1) we have obtained the Lewis structure of PF5 previously

.....
.....
.....
.....
.....
.

.
.....
.....
.....
.....
.....

P
...
...
...
...
...
...

....
.....
.....
.....
.
.
.
....

.....
.....
.....
.....
.....
.

F


F

(2) VSEPR notation: AB5

GChem I

10.2

(3) electron-pair geometry: trigonal bipyramidal

(4) no lone pairs molecular geometry electron-pair geometry: trigonal bipyramidal
Exercise: Determine the shape of SF4
(1) Lewis structure

A = 1 6 + 4 7 = 34
N = 5 8 = 40
S = N A = 40 34 = 6

F

.....
.....
.....
.....
.....
.

..
.....
.....
.....
.....
.
.
.
.

.
.....
.....
.....
....
.
.
.
..

.....
.....
.....
.....
.....
.

3 bonds =

S %8

F


F

S has expanded valence

(2) VSEPR notation: AB4 E
(3) electron-pair geometry: trigonal bipyramidal
(4) lone pair molecular geometry 6 electron-pair geometry
molecular geometry: seesaw (sawhorse, distorted tetrahedron)
GChem I

10.3

Exercise: Determine the shape of NF3

(1) Lewis structure

A = 1 5 + 3 7 = 26
N = 4 8 = 32
S = N A = 32 26 = 6

3 bonds

F
....
...
..
...
...

.
.....
.....
.....
.....
.....

.....
.....
.....
.....
.....
.

(2) VSEPR notation: AB3 E

(3) electron-pair geometry: tetrahedral
(4) lone pair molecular geometry 6 electron-pair geometry
molecular geometry: trigonal pyramidal
Exercise: Determine the shape of carbon suboxide C3 O2
(1) Lewis structure

A = 2 6 + 3 4 = 24
GChem I

10.4

N = 5 8 = 40
S = N A = 40 24 = 16

..........................
..........................

..........................
..........................

..........................
..........................

8 bonds

=
..........................
..........................

(2) VSEPR notation for each carbon atom: AB2

(3) electron-pair geometry: linear
(4) no lone pairs molecular geometry electron-pair geometry
molecular geometry: linear

O
O
O
Exercise: Determine the shape
of ozone O3
..........................
..........................

..........................

(1) Lewis structure

A = 3 6 = 18
N = 3 8 = 24
S = N A = 24 18 = 6

..........................
..........................

..........................

3 bonds

..........................

..........................
..........................

(2) VSEPR notation for the central oxygen atom: AB2 E

Typeset by FoilTEX
GChem I

1
10.5

(3) electron-pair geometry: trigonal planar

(4) lone pair molecular geometry 6 electron-pair geometry
molecular geometry: bent (angular)

expected bond angle: 120 ; experimental value: 117

polar molecules
polar covalent bond
example:
+

H Cl
+
d
measure of the charge separation (or polarity) is the dipole moment

= d
unit of dipole moment [] = Cm
too large, use the unit debye ( D) for molecules

1 D = 3.34 1030 Cm
experiments show that CO2 is nonpolar; however the molecule
has polar covalent bonds since the electronegativity of C is 2.5
and that of O is 3.5
GChem I

10.6

why is carbon dioxide nonpolar??

consider the shape of the molecule
the Lewis structure is the same as that of CS2 (Set 9)

..........................
..........................

..........................
..........................

VSEPR notation: AB2 = molecular geometry = linear

O


2+
..........................
..........................

..........................
..........................

+
=0

dipole moment of a molecule depends on the shape of the molecule

water molecule: O: EN = 3.5, H: EN =2.1
polar bonds exist in H2 O
shape of H2 O
(1) Lewis structure

A = 21+16 = 8
N = 2 2 + 1 8 = 12
S = N A = 12 8 = 4
GChem I
Typeset by FoilTEX

2 bonds
10.7

..........................

..........................

(2) VSEPR
AB
H notation:
O
H 2 E2
..........................

..........................

(3) electron-pair geometry: tetrahedral

(4) lone pairs molecular geometry 6 electron-pair geometry
molecular geometry: bent (angular)
bond angle: 104

O
+ H+

 6@
I
@

H +

@+

6=0

net dipole moment = 1.94 D

molecules of the type ABn are NOT polar if all terminal atoms B
are the same.
Examples:

CH4

AB4

nonpolar

Typeset by FoilTEX

CH3 Cl

AB4

polar

Typeset by FoilTEX
GChem I

1
10.8

different theories of the chemical bond

Lewis: simple; relies on electron pairs = problems: O2 , oddelectron species, resonance
VSEPR: predicts molecular shape; relies on electron pairs
Quantum Mechanics
valence-bond theory: covalent bond = overlap of atomic orbitals

H2
H2 S
provides information on bond energies: 1s -1s overlap is stronger
than 1s -3p overlap

[He]

2s

2p

= simplest hydrocarbon CH2 with bond angle of 90

! CH2 does not exist!
simplest hydrocarbon: methane CH4
???
excited-state
GChem I

10.9

[He]

2s

2p

promotion: 2s 2p
problem: 2s nondirectional, 2p at right angles
Lewis structure of methane

H
...
...
..
...
...
.

..........................

..........................

...
...
...
...
...
...

H
VSEPR: AB4 = tetrahedral (electron-pair and molecular geom

etry) = bond angle 109.5 6= 90

???
we cannot solve the Schrdinger equation to obtain an exact,
analytical expression for the molecular wave function
atomic orbitals approximation of for multielectron atoms
this approximation does not work well for molecules; find a better approximation:
hybridization
GChem I

10.10

2s + 3 2p = 4sp 3 hybrid orbitals

ammonia NH3
Lewis

..........................

..........................

...
...
...
...
...
...

H
VSEPR: AB3 E = electron-pair geometry: tetrahedral (molecular
3
geometry: trigonal pyramidal) = hybrid: sp

2p
2s

sp 3

N
H

H
H

GChem I
Typeset by FoilTEX

10.11
1

water H2 O
Lewis

..........................

..........................

VSEPR: AB2 E2 = electron-pair geometry: tetrahedral (molecu3

lar geometry: bent) = hybrid: sp

2p
2s

sp 3

H
O
H

BF3

AB3

electron-pair geometry: trigonal planar

2

3 sp hybrid orbital + 1 p orbital

BeCl2

AB2

electron-pair geometry: linear

Typeset by FoilTEX
GChem I

1
10.12

H
H
2 sp hybrid orbital + 2 p orbital
ethene (ethylene) C2 H4
Lewis

....
...
..
...
....

....
...
..
...
....

..........................
..........................

...
...
...
...
...
...

...
...
...
...
...
...

each C: AB3
electron-pair geometry: trigonal planar

= hybrid: sp 2 + 1 p
-bond: overlap on the internuclear axis
2

for ethene: 1s (1)sp and (1)sp (1)sp

-bond: overlap off the internuclear axis

Typeset by
FoilTE
-bond
weaker
than
aX

for ethene: p p
double bond = -bond + -bond
GChem I

10.13

stronger than a single bond (-bond), but not twice as strong

shape of a molecule: determined by -bond framework
rotation about a double bond is severely restricted
ethyne (acetylene) C2 H2
Lewis

..........................

..........................
..........................
..........................

..........................

each C: AB2
electron-pair geometry: linear

= hybrid: sp + 2 p
triple bond: 1 -bond + 2 -bonds
still no explanation why O2 is paramagnetic
fourth description of chemical bond:
molecular-orbital theory (MO)
use wave functions or orbitals that belong to the entire molecule

H2 molecule: 1s + 1s

GChem I

1s

antibonding

&

1s

bonding
10.14

a bonding molecular orbital has lower energy than the atomic

orbitals from which it was formed
lower energy = greater stability
bonding orbital: electron density greatest between the two nuclei
formation of bonding orbital: constructive interference
an antibonding molecular orbital has higher energy than the
atomic orbitals from which it was formed
higher energy = lower stability
antibonding orbital: electron density goes to zero between the
two nuclei
formation of bonding orbital: destructive interference
sigma molecular orbital: electron density is concentrated on the
internuclear axis, cylindrical symmetry
Molecular Electron Configuration (molecular-orbital diagram)
1. The number of molecular orbitals formed = number of atomic
orbitals combined
2. The more stable the bonding orbital, the less stable the corresponding antibonding orbital
GChem I

10.15

3. Aufbau principle (filling of MOs proceeds from low to high energies)

4. Pauli exclusion principle (at most two electrons per MO, opposite spins)
5. Hunds rule (when MOs of identical energy are available,
electrons occupy those orbitals singly if possible and have
the same spin orientation)
6. Number of electrons in MOs = total number of electrons on
the bonding atoms
bond order = 12 (# of electrons in bonding MOs # of electrons
in antibonding MOs)
a molecule is stable if the bond order is greater than zero
First and Second Period Homonuclear Diatomic Molecules
hydrogen molecule H2
atomic hydrogen H 1s

= H2 two electrons
2

molecular electron configuration of H2 : (1s )

bond order = 21 (2 0) = 1
helium molecule He2

He 1s 2 = He2 four electrons

GChem I

10.16

molecular electron configuration of He2 : (1s ) (1s )

bond order = 12 (2 2) = 0
the helium dimer does not exist
lithium dimer Li2

Li 1s 2 2s 1 = Li2 six electrons

2

molecular electron configuration of Li2 : (1s ) (1s ) (2s )

bond order = 12 (2 + 2 2) = 1
stable diamagnetic molecule; found in vapor phase
beryllium dimer Be2

Be 1s 2 2s 2 = Be2 eight electrons

2

molecular electron configuration of Be2 : (1s ) (1s ) (2s ) (2s )

bond order = 12 (2 + 2 2 2) = 0
beryllium dimer is unstable
boron dimer B2

B 1s 2 2s 2 2p 1 = B2 ten electrons
p -orbitals come into play
GChem I

10.17

2p , 2p

2p , 2p

molecular-orbital energy level diagram

2

molecular electron configuration of B2 : (1s ) (1s ) (2s ) (2s ) (2p )

(1s )2 (1s )2 (2s )2 (2s )2 (2p y )1 (2p z )1

bond order = 12 (2 + 2 + 2 2 2) = 1
stable paramagnetic molecule
molecular-orbital diagrams for 2nd period homonuclear diatomic
molecules
oxygen molecule

O2 : (1s )2 (1s )2 (2s )2 (2s )2 (2p x )2 (2p y )2 (2p z )2 (2p y )1 (2p z )1

bond order = 12 (2 + 2 + 2 + 2 + 2 2 2 2) = 2
stable paramagnetic molecule
molecular orbital theory explains the magnetic properties of
the oxygen molecule and other diatomic molecules and ions

GChem I

10.18