Bonding Theories

Bonding Theories:
Valence Bond Theory

Molecular Orbital Theory
Tro: Chemistry: A Molecular Approach, 2/e Copyright © 2011 Pearson Education, Inc.
Lewis Theory: Electron Groups and
Molecular Shapes
There are Regions of electrons in an atom:
• Some from placing shared pairs of valence
electrons between bonding nuclei;
• Other from placing lone pairs valence
electrons on a single nuclei
Regions of electron groups should repel each
other (VSEPR) and determines the molecular
shape and molecular polarity
Tro: Chemistry: A Molecular Approach, 2/e 2 Copyright © 2011 Pearson Education, Inc.
Problems with Lewis Theory
• Useful predicting trends, but not quantitative
e.g. bond angles, bond strength, bond length
• Can not give one correct structure for many

molecules where resonance is important
• Often does not predict the correct magnetic

behavior of molecules
✓ e.g. O2 is paramagnetic, though the Lewis
structure predicts it is diamagnetic
Valence Bond Theory. I
Linus Pauling et al:
• Chemical bonds form when the orbitals (wave
functions of electrons in the atoms) on those
atoms interact (overlap)
• The kind of interaction depends on whether the

orbitals align along the axis between the nuclei,
or outside the axis
Orbital Interaction
As two atoms approach, the half-filled valence
atomic orbitals on each atom would interact and
become more stable: covalent bonds
Covalent bonds
are regions of
high probability of
finding the
shared electrons
in the molecule
Orbital interaction Stabilizes the molecule
• Forming covalent bond would
stabilize the molecule because
they would contain paired
Potential energy
e- e-
electrons shared by both
atoms
✓Attraction between the
shared electrons and the e-
e-
nuclei > Repulsion between
the nuclei
Atomic Orbital in the Bonding of H2S
H
↑↓ H─S bond
1s ↑
+ ↑↓ ↑ ↑ ↑↓ S
1s ↑ 3s 3p
↑↓ H─S bond
H
Predicts bond angle = 90°

Actual bond angle = 92°
Valence Bond Theory I – Problem
Many molecules such as methane (tetrahedral,
bond angle = 109.5°) can not be explained by
half-filled atomic orbitals
✓C = 2s22px12py12pz0 would predict two or

three bonds that are 90° apart
Valence Bond Theory II:
Orbital Hybridization
1. When forming covalent bonds, each valence
electron can reside in either standard s, p, d,
and f orbitals, or in hybridized orbitals of
these atomic orbitals.
2. Covalent bond forms via half-filled atomic
orbitals interacting, ONE pair of electrons
(↑↓) in the new bonding orbital
3. Shape of the molecule determined by the
geometry of the interacting orbitals
Hybridization
+ =
• Some atoms hybridize their orbitals to

maximize bonding
• Hybridization: mixing different types of
orbitals in the valence shell to make a new
set of degenerate (equal energy) orbitals
✓1 x s orbital + 2 x p orbital = 3 x sp2 hybrid orbital
• Same type of atom can have different types
of hybridization
✓C = sp, sp2, sp3
Hybrid Orbitals
• The number of standard atomic orbitals
combined = the number of hybrid orbitals
formed
✓combining a 2s with a 2p gives 2 x sp
hybrid orbitals
✓H cannot hybridize!!
➢its valence shell only has one orbital
• The number and type of standard atomic

orbitals combined determines the shape of
the hybrid orbitals
Orbital Diagram of sp3 Hybridization in C
Orientation of sp3 Hybridized Orbitals
Methane: Hydrogen bonded with sp3-
hybridized Carbon
Various Carbon Hybridizations
Unhybridized   
2s 2p
sp hybridized    
2sp 2p
sp2 hybridized    
2sp2 2p
sp3 hybridized    
2sp3
sp3 Hybridization
• Atom with _____ electron groups around it

✓tetrahedral geometry
✓109.5° angles between hybrid orbitals
• Atom uses hybrid orbitals for all bonds and
lone pairs
sp3 Hybridized Atoms
Orbital Diagrams
• Place electrons into hybrid and unhybridized valence orbitals
as if all the orbitals have equal energy
• Lone pairs generally occupy hybrid orbitals
Unhybridized atom sp3 hybridized atom
   C    
2s 2p 2sp3
      

N 
2s 2p 2sp3
Bonding with Valence Bond Theory
According to valence bond theory, bonding takes

place between atoms when their atomic or hybrid
orbitals interact (“overlap”). To interact,
• The orbitals must either be aligned along the
axis between the atoms. A B
or
• The orbitals must be parallel to each other and
perpendicular to the interatomic axis
A B
Ammonia Formation with sp3 N
Sigma (s) bond
• The interacting atomic orbitals point along the axis
connecting the two bonding nuclei
✓ either standard atomic orbitals or hybrids
➢ s–to–s, p–to–p, hybrid–to–hybrid, s–to–hybrid, etc.
pi (p) bond
• Definition: The bonding atomic orbitals are parallel
to each other and perpendicular to the axis
connecting the two bonding nuclei
✓ between unhybridized parallel p orbitals
• Double bond = one s bond + one p bond

• Triple bond = one s bond + two p bonds
• Strength of orbital overlap: s bonds > p bonds
sp2
• Atom with _____ electron
groups around it
✓ trigonal planar system
➢ C = trigonal planar
➢ N = trigonal bent
➢ O = “linear”
✓ 120° bond angles
✓ flat
• Atom uses hybrid orbitals for
s bonds and lone pairs, uses
nonhybridized p orbital for p
bond
sp2 Hybridized Atoms
Orbital Diagrams
Unhybridized atom sp2 hybridized atom
C
   3s    
1p
2s 2p 2sp2 2p
N
      

2s 
2s 2p 1p 2sp2 2p
O
Formaldehyde, CH2O Orbital
C Diagram
H H
p
pC   pO
s
sp2 C       sp2 O
s s
 
1s H 1s H
Hybrid orbitals
overlap to form a
s bond.
Unhybridized p
orbitals overlap
to form a p bond.
CH2NH Orbital Diagram
p
pC   pN
s
sp2 C       sp2 N
H
s s C N s
  H H 
1s H 1s H 1s H
Does Bond Rotation Affect Bonding?
 s bond forms along the internuclear axis, rotation
around that bond does not affect the interaction
between the orbitals.
 p bond interacts above and below the internuclear
axis, so rotation around the axis requires the
breaking of the interaction between the orbitals
p bond p bond broken
s bond s bond unaffected
Bond Rotation: s bond vs. p bond
Rigidity of double bonds leads to TWO
different compounds
Different Polarity (dipole moment), Density, melting
points, boilding points:
sp hybridization
• Atom with _____ electron groups
✓linear shape
✓180° bond angle
• Atom uses hybrid orbitals for s bonds or lone
pairs, uses nonhybridized p orbitals for p bonds
p
s
p
HCN Orbital Diagram
2p
pC     pN
s
sp C     sp N
1s H
sp Hybridized Atoms
Orbital Diagrams
Unhybridized atom sp hybridized atom

C
   2s    
2p
2s 2p 2sp 2p
N
      

1s 
2s 2p 2p 2sp 2p
sp3d
• Atom with five electron groups
✓trigonal bipyramid electron
geometry
✓Seesaw, T–Shape, Linear
✓120° & 90° bond angles
• Use empty d orbitals from

valence shell
• d orbitals can be used to
make p bonds
sp3d Hybridized Atoms
Orbital Diagrams
Unhybridized atom sp3d hybridized atom
    P     
3s 3p 3d 3sp3d
    S     
3s 3p 3d 3sp3d
(non-hybridizing d orbitals not shown)
SOF4 Orbital Diagram
p
dS   pO
s
sp3d S         sp2 O
s s s s
   
2p F 2p F 2p F 2p F
sp3d2
• Atom with six electron groups
around it
✓octahedral electron geometry
✓Square Pyramid, Square Planar
✓90° bond angles
• Use empty d orbitals from
valence shell to form hybrid
• d orbitals can be used to make
p bonds
sp3d2 Hybridized Atoms
Orbital Diagrams
Unhybridized atom sp3d2 hybridized atom
↑↓ ↑↓ ↑ ↑ S ↑ ↑ ↑ ↑ ↑ ↑
3s 3p 3d 3sp3d2
↑↓ ↑↓ ↑↓ ↑ I ↑↓ ↑ ↑ ↑ ↑ ↑
5s 5p 5d 5sp3d2
(non-hybridizing d orbitals not shown)
Predicting Hybridization and
Bonding Scheme
1. Start by drawing the Lewis structure
2. Use VSEPR Theory to predict the electron
group geometry around each central atom
3. Select the hybridization scheme based on
the electron group geometry
4. Sketch the atomic and hybrid orbitals on the
atoms in the molecule, showing overlap of
the appropriate orbitals
5. Label the bonds as s or p
Example: Predict the hybridization and
bonding scheme for CH3CHO
Draw the Lewis structure
Predict the electron group C1 = 4 electron areas

geometry around inside  C1= tetrahedral
atoms C2 = 3 electron areas
 C2 = trigonal planar
Predict the hybridization and bonding
scheme for CH3CHO
Determine the C1 = tetrahedral
hybridization of the  C1 = sp3
interior atoms C2 = trigonal planar
 C2 = sp2
Sketch the molecule and
orbitals
Predict the hybridization and bonding
scheme for CH3CHO
Label the bonds
Practice – Predict the hybridization of all
the atoms in H3BO3
H = can’t hybridize
B = 3 electron groups = sp2
O = 4 electron groups = sp3
Practice – Predict the hybridization and
bonding scheme of all the atoms in NClO
•• •• ••
•O N Cl ••
•
•• s:Osp2─Nsp2
↑↓ ↑↓
N = 3 electron groups = sp2 O ↑↓ N

↑↓ s:Nsp2─Clp
↑↓
O = 3 electron groups = sp2
Cl = 4 electron groups = sp3 ↑↓ Cl
O N
p:Op─Np
Cl
Problems with Valence Bond Theory
• VB theory predicts many properties better than
Lewis theory
✓bonding schemes, bond strengths, bond lengths,
bond rigidity
• However, VB theory doesn’t predict many other
properties
✓magnetic behavior of O2
• In addition, VB theory treats the electrons as
localized in orbitals on the atoms in the
molecule
• In MO theory, solving Schrödinger’s

wave equation to calculate a set of
molecular orbitals
• In this treatment, the electrons belong to
the whole molecule – so the orbitals
belong to the whole molecule
✓ delocalization
LCAO
• The simplest guess starts with the atomic
orbitals of the atoms adding together to
make molecular orbitals – this is called the
Linear Combination of Atomic Orbitals
method
✓weighted sum
• Because the orbitals are wave functions,
the waves can combine either
constructively or destructively
Molecular Orbitals
• Wave functions combine constructively forms
molecular orbital _____ energy than the original
atomic orbitals → Bonding Molecular Orbital
✓ s, p
✓ most of the electron density between the nuclei
• Wave functions combine destructively forms

molecular orbital ______ energy than the original
atomic orbitals→ Antibonding Molecular Orbital
✓ s*, p*
✓ most of the electron density outside the nuclei
✓ nodes between nuclei
Interaction of 1s Orbitals: Bonding vs.
Antibonding
• Electrons in bonding MOs are stabilizing
✓lower energy than the atomic orbitals
• Electrons in antibonding MOs are
destabilizing
✓higher in energy than atomic orbitals
✓electron density located outside the
internuclear axis
✓electrons in antibonding orbitals cancel
stability gained by electrons in bonding orbitals
Energy Comparisons of Atomic Orbitals
to Molecular Orbitals
MO and Properties
• Bond Order = difference between number of
electrons in bonding and antibonding orbitals
✓ only need to consider valence electrons
✓ may be a fraction
✓ higher bond order = stronger and shorter bonds
✓ if bond order = 0, then bond is unstable compared to
individual atoms and no bond will form
• Paramagnetic: unpaired electrons in MO

✓ if all electrons paired it is diamagnetic
Dihydrogen, H2
Molecular
Hydrogen Hydrogen
Orbitals
Atomic Atomic
Orbital Orbital
s*
1s 1s
s
Because more electrons are in

bonding orbitals than are in antibonding orbitals,
net bonding interaction
H2
s* Antibonding MO
LUMO
s bonding MO
HOMO
Dihelium, He2
Molecular
Helium Helium
Orbitals
Atomic Atomic
Orbital Orbital
s*
1s 1s
s
BO = ½(2-2) = 0
Because there are as many electrons in

antibonding orbitals as in bonding orbitals,
there is no net bonding interaction
Lithium Dilithium, Li2 Lithium
Atomic Molecular Atomic
Orbitals Orbitals Orbitals
s*
2s 2s
s Any fill energy level will
generate filled bonding
and antibonding MO’s;
BO = ½(4-2) = 1 s* therefore only need to
consider valence shell
1s 1s
Because more electrons are s
in bonding orbitals than are in
antibonding orbitals, there is a
Li2
s* Antibonding MO
s bonding MO LUMO
HOMO
Interaction of p Orbitals
Interaction of p Orbitals
O2
• Dioxygen is paramagnetic
• Paramagnetic material has unpaired electrons
• Neither Lewis theory nor valence bond theory
predict this result
O2 as Described by Lewis and
VB Theory
s*
Oxygen Oxygen
Atomic Atomic
Orbitals p* Orbitals
2p O2 MO’s 2p
more electrons are in
bonding orbitals than are
p
in antibonding orbitals:
s 2 x unpaired electrons in the
antibonding orbitals,
O2 as paramagnetic
BO = ½(8 be – 4 abe) s*
BO = 2
2s 2s
s
Example: N2− : bond order and magnetic
properties
Bond order =
(#bonding
BO = ½(8 be – 3 s*2p
electrons - abe)
#antibonding BO = 2.5 ↑ p*2p
electrons) ÷ 2
This is lower than BO
of N2 (3), the bond ↑↓ s2p
should be weaker
Unpaired
↑↓ ↑ ↓ p2p
Presence of electrons:
unpaired paramagnetic ↑↓ s*2s
electrons →
paramagnetic
↑↓ s2s
Heteronuclear Diatomic Molecules & Ions
• When the combining atomic orbitals are
identical and equal energy, the contribution of
each atomic orbital to the molecular orbital is
equal
• When the combining atomic orbitals are
different types and energies, the atomic
orbital closest in energy to the molecular
orbital contributes more to the molecular
orbital
Heteronuclear Diatomic Molecules & Ions
• The more electronegative an atom is, the
lower in energy are its orbitals
• Lower energy atomic orbitals contribute
more to the bonding MOs
• Higher energy atomic orbitals contribute
more to the antibonding MOs
• Nonbonding MOs remain localized on the
atom donating its atomic orbitals
Example: Draw a molecular orbital diagram of N2−
ion and predict its bond order and magnetic
properties
Write a MO s*2p
diagram for N2−
using N2 as a N has 5 valence
base electrons ↑ p*2p
Count the
number of 2 N = 10e−
valence (−) = 1e− ↑↓ s2p
electrons and total = 11e−
assign these to
the MOs
↑↓ ↑ ↓ p2p
following the
aufbau
principle, Pauli ↑↓ s*2s
principle &
Hund’s rule ↑↓ s2s
NO
a free radical
s2s Bonding MO BO = ½(6 be – 1 abe)

shows more BO = 2.5
electron density
near O because
it is mostly O’s
2s atomic orbital
Practice – Draw a molecular orbital diagram of C2+
and predict its bond order and magnetic properties
Practice – Draw a molecular orbital diagram of C2+
and predict its bond order and magnetic properties
C has 4 valence
electrons s*2p
2 C = 8e− p*2p
(+) = −1e−
total = 7e−
s2p
BO = ½(5 be – 2 abe)
BO = 1.5 ↑↓ ↑ p2p
Because there
are unpaired ↑↓ s*2s
electrons, this ion
is paramagnetic ↑↓ s2s
HF
Polyatomic Molecules
• When many atoms are combined together, the

atomic orbitals of all the atoms are combined to
make a set of molecular orbitals, which are
delocalized over the entire molecule
• Gives results that better match real molecule
properties than either Lewis or valence bond
theories
Ozone, O3
MO Theory:
Delocalized
p bonding
orbital of O3

Bonding Theories

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Bonding Theories

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Bonding Theories:

Valence Bond Theory

• Can not give one correct structure for many

• Often does not predict the correct magnetic

• The kind of interaction depends on whether the

Predicts bond angle = 90°

✓C = 2s22px12py12pz0 would predict two or

• Some atoms hybridize their orbitals to

• The number and type of standard atomic

• Atom with _____ electron groups around it

Unhybridized atom sp3 hybridized atom

According to valence bond theory, bonding takes

• Double bond = one s bond + one p bond

• Strength of orbital overlap: s bonds > p bonds

s bond s bond unaffected

Unhybridized atom sp hybridized atom

• Use empty d orbitals from

Predict the electron group C1 = 4 electron areas

N = 3 electron groups = sp2 O ↑↓ N

• In MO theory, solving Schrödinger’s

• Wave functions combine destructively forms

• Paramagnetic: unpaired electrons in MO

Because more electrons are in

Because there are as many electrons in

s2s Bonding MO BO = ½(6 be – 1 abe)

• When many atoms are combined together, the

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