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1) The document discusses valence bond theory (VBT), which describes bonding using localized atomic orbitals. VBT can explain Lewis structures and predicts σ and π bonds. 2) Heitler-London wavefunctions were developed to describe H2 bonding using 1s atomic orbitals. Variation principles can optimize wavefunctions to minimize energy. 3) Hybrid atomic orbitals were introduced by Pauling to describe molecular geometry and hybridization through combinations of s and p orbitals.

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0% found this document useful (0 votes)
66 views32 pages

13 PDF

1) The document discusses valence bond theory (VBT), which describes bonding using localized atomic orbitals. VBT can explain Lewis structures and predicts σ and π bonds. 2) Heitler-London wavefunctions were developed to describe H2 bonding using 1s atomic orbitals. Variation principles can optimize wavefunctions to minimize energy. 3) Hybrid atomic orbitals were introduced by Pauling to describe molecular geometry and hybridization through combinations of s and p orbitals.

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Bheim Llona
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
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Chem 104A, UC, Berkeley

Chem 104A, UC, Berkeley

Molecular Orbital

Reading: DG 2.11-14, 3.1-5, 4; MT 3.1


Lewis Structure

G. N. Lewis (UC, Berkeley, 1915)

Octet Rule: Closed shell configuration of 8 surrounding e

1
Chem 104A, UC, Berkeley

Resonance

The best structure has the fewest formal charges and has
the negative charge on the highest electronegativity atom.

Chem 104A, UC, Berkeley

Valence Bond theory

Heitler, London (1927)

L. Pauling (orbital hybridization)


Localized orbital approach

Investigating ground state molecules,


molecular geometry
Bond dissociation energy

2
Chem 104A, UC, Berkeley

Molecular Orbital theory

Mulliken

Delocalized orbital approach

Unoccupied orbital

Spectroscopic properties
(ionization, excited states)

Chem 104A, UC, Berkeley


Valence Bond Theory
Valence bond theory (VBT) is a localized quantum mechanical approach
to describe the bonding in molecules. VBT provides a mathematical
justification for the Lewis interpretation of electron pairs making bonds
between atoms. VBT asserts that electron pairs occupy directed orbitals
localized on a particular atom. The directionality of the orbitals is
determined by the geometry around the atom which is obtained from the
predictions of VSEPR theory.

In VBT, a bond will be formed if there is overlap of appropriate orbitals on


two atoms and these orbitals are populated by a maximum of two electrons.

 bonds: have
 bonds: a node on the
symmetric about inter-nuclear axis
the internuclear and the sign of
axis the lobes
changes across
the axis.

3
Chem 104A, UC, Berkeley
Valence Bond Theory
Valence bond theory treatment of bonding in H2 and F2

F
2s 2p
HA 1s1 HB 1s1
F
A  B  2s 2p

z axis

2pz 2pz

This gives a 1s-1s  bond This gives a 2p-2p  bond between


between the two H atoms. the two F atoms.

For the VBT treatment of bonding, we ignore the anti-bonding.

Chem 104A, UC, Berkeley


Valence bond theory treatment of bonding in O2

z axis O
2s 2p
2pz 2pz
This gives a 2p-2p  bond O
between the two O atoms. 2s 2p

z axis
O O
Lewis structure

2py 2py (the choice of 2py is arbitrary)


Double bond:  bond +  bond
Triple bond:  bond + 2  bonds
This gives a 2p-2p  bond between
the two O atoms. In VBT,  bonds
The Lewis approach and VBT
are predicted to be weaker than 
predict that O2 is diamagnetic –
bonds because there is less overlap.
this is wrong!

4
Chem 104A, UC, Berkeley

Valence Bond theory

A B

0.74 A

Bond dissociation energy: 103 kcal/mol

Chem 104A, UC, Berkeley

Our Goal

Use atomic orbitals to compose a wavefunction


that accurately describe these observations.

5
Chem 104A, UC, Berkeley
1 1 3 / 2  r / a0
Energy 1s  ( ) e
 a0

a
  1s A (1) 1sB (2)
0

-2

f Experimental curve
-4 eV

0.5 1.0 1.5 Internuclear distance

1 1 3 / 2  r / a0 Chem 104A, UC, Berkeley


Energy 1s  (
) e
 a0
g    1s A (1) 1sB (2)  1s A (2) 1s B (1)

a
b
0

   1s A (1) 1sB (2)  1s A (2) 1sB (1)


-2
Heitler-London Wavefunction

f Experimental curve
-4 eV

0.5 1.0 1.5 Internuclear distance

6
Chem 104A, UC, Berkeley

Variation Principle:

If an arbitrary wavefunction is used to


calculate the energy, then the value obtained
is never less than the true value.

  ( x) H ( x)dx
*

H 
  * ( x) ( x)

Chem 104A, UC, Berkeley

Variation Principle:

If an arbitrary wavefunction is used to


calculate the energy, then the value obtained
is never less than the true value.

 (x)
Can always minimize E ( x ) ( x)

7
Chem 104A, UC, Berkeley
1 1 3 / 2  r / a0
1s  () e
 a0

+ +

1 Z 3 / 2  Zr / a0
1s   100  () e
 a0

Chem 104A, UC, Berkeley


1 Z 3 / 2  Zr / a0
Energy 1s  () e
 a0
g

a
b
0 c
   1s A (1) 1sB (2)  1s A (2) 1sB (1)
-2 Zeff=1.17

f Experimental curve
-4 eV

0.5 1.0 1.5 Internuclear distance

8
Chem 104A, UC, Berkeley
Promoting electron
Orbital Hybridization

- + +
A
1s A
2pzA  A  N (1s A   2 p zA )
 B  N (1sB   2 p zB )
+ + - B
1s B
2pzB
1
1  2
s contribution

2
p contribution
1  2

Chem 104A, UC, Berkeley

- + +  A  N (1s A   2 p zA )
A
1sa 2pza

B
+ + -
 B  N (1s B   2 p zB )
1sb 2pzb

=0.1

9
Chem 104A, UC, Berkeley
Energy
 A  N (1s A   2 p zA )
g
 B  N (1sB   2 p zB )

a
b
0 c

-2 d    A (1)   B (2)   A (2)   B (1)


f Experimental curve
-4 eV

0.5 1.0 1.5 Internuclear distance

Chem 104A, UC, Berkeley


Energy

a
b
0 c

   A (1)   B (2)   A (2)   B (1)


-2 d
e  [ A (1)   A (2)   B (2)   B (1)]

f Experimental curve
=6%
-4 eV

0.5 1.0 1.5 Internuclear distance

10
Chem 104A, UC, Berkeley
Energy Valence bond theory is all about promoting e
and hybridizing orbitals into the shape required by
experiments.! g

a
b
0 c

-2 d
e
f
-4 eV

0.5 1.0 1.5 Internuclear distance

Chem 104A, UC, Berkeley

Covalent Bond
-  F  N (2 p zF   2s F )
+ +
+ + H1s
2sF 2pzF
lp  N (2 p zF   2sF )
- + +
+ H
+

2sF 2pzF
=0.5 Lone pair

11
Chem 104A, UC, Berkeley

promotion

1s 2 2s 2 2 p x2 2 p y2 2 p1z  1s 2 2 s1 2 p x2 2 p y2 2 p z2

E  500kcal / mol
1 eV=96.4 kJ/mol=23.1 kCal/mol
Benefit of hybridization
1. Increase in e density between nuclei, enhanced bonding
2. Decrease in e-e repulsion by formation of a lone-pair
orbital, LP Orbital more directed away from BP than the
Original s LP

Ionic Contribution: 50%


  1sH (1) F (2)  1sH (2) F (1)   F (2) F (1)

Chem 104A, UC, Berkeley

12
Chem 104A, UC, Berkeley

  [1sHa (1)2 p yo (2)  1sHa (2)2 p yo (1)]  [1sHb (3)2 p zo (4)  1sHb (4)2 p zo (3)]

Chem 104A,
Valence bond theory is all about promoting UC, Berkeley
electron
and hybridizing orbitals into the shape required by
experiments!

-
y py s
+ O -
  104.5
+ pz
H H
    dv  0
b
a b

a
 a dv  1
 2

13
Chem 104A, UC, Berkeley

-
y py s
+ O -

+ pz
H H

a b
z
 
 a  N [cos  2 p zo  sin  2 p yo    2so ]
2 2
 
b  N [cos  2 p zo  sin  2 p yo    2so ]
2 2

Orthogonality andChem 104A, UC, Berkeley


Normalization
Two properties of acceptable orbitals (wavefunctions) that we have not yet
considered are that they must be orthogonal to every other orbital and they
must be normalized. These conditions are related to the probability of finding
an electron in a given space.
Orthogonal means that the integral of the product of an orbital with any other
orbital is equal to 0, i.e.:
     0
n m
where n  m and  means that the integral
is taken over “all of space” (everywhere).

Normal means that the integral of the product of an orbital with itself is equal
to 1, i.e.:
     1
n n

This means that we must find normalization coefficients that satisfy


these conditions. Note that the atomic orbitals () we use can be
considered to be both orthogonal and normal or “orthonormal”.

14
  Chem 104A, UC, Berkeley
 a  N [cos  2 p zo  sin  2 p yo    2so ]
2 2
 
b  N [cos  2 p zo  sin  2 p yo    2so ]
2 2

  104.5    dv  0
a b
Orthogonality

  0.5
 dv  1
 2
Normalization
a N  1 / 1.25

 a  0.55  2 p zo  0.71  2 p yo  0.452  2so


b  0.55  2 p zo  0.712  2 p yo  0.452  2 so

  [1sHa (1)2 p yo (2)  1sHa (2)2 p yo (1)]  [1sHb (3)2 p zo (4)  1sHb (4)2 p zo (3)]
New Wavefunction:
  [1sHa (1) a (2)  1sHa (2) a (1)]  [1sHb (3)b (4)  1sHb (4)b (3)]

Chem 104A, UC, Berkeley

Unit Orbital Contribution:

The contribution of any atomic orbital to all hybrid


Orbitals must add up to 1.0.

15
 a  0.55 Chem
 2 p zo 104A,
 0.71  2Berkeley
UC, p yo  0.452  2so
Orbital contribution   0.55  2 p  0.712  2 p  0.452  2s
b zo yo o

a b
30% 30% 60%
2 p zo 0.55  30%
2

50% 50% 100%


2 p yo 0.712  50%

20% 20% 40%


2 so 0.452  20%
2

Bonding: Average 80% p character, 20% s character


What’s left? 40% p +60% s
lp  0.63  2 p zo  0.77  2 so

Chem 104A, UC, Berkeley

-
y py s
+ O - lp  0.63  2 p zo  0.77  2so
+ pz
H H

a b
z

 a  0.55  2 p zo  0.71  2 p yo  0.452  2so


b  0.55  2 p zo  0.712  2 p yo  0.452  2 so

16
Chem 104A, UC, Berkeley

p s
1
lp1  (2 p x   lp ) character character
2
lp1 
1
(2 p x   lp ) Bonding 80% 20%
2 orbital
lp 70% 30%
orbital

Chem 104A, UC, Berkeley


Directionality
The bonding in diatomic molecules is adequately described by combinations
of “pure” atomic orbitals on each atom. The only direction that exists in such
molecules is the inter-nuclear axis and the geometry of each atom is
undefined in terms of VSEPR theory (both atoms are terminal). This is not
the case with polyatomic molecules and the orientation of orbitals is important
for an accurate description of the bonding and the molecular geometry.

Examine the predicted bonding in ammonia using “pure” atomic orbitals:

2s 2p
N

The 2p orbitals on N are oriented along the X, Y,


3H and Z axes so we would predict that the angles
1s 1s 1s between the 2p-1s  bonds in NH3 would be 90°.
We know that this is not the case.
H N H
H

17
Chem 104A, UC, Berkeley

H  N  H  107.3
p s
character character
Bonding 77% 23%
orbital
lp 69% 31%
orbital

Chem 104A, UC, Berkeley

1s 2 2 s 2 2 p 0 Promotion 1s 2 2s1 2 p1

1
Chem 104A, UC, Berkeley

1
a  (2 s  2 p x )
2

1
b  (2s  2 px )
2
p s
character character
Bonding 50% 50%
orbital

Chem 104A, UC, Berkeley

2
Chem 104A, UC, Berkeley

HybridizationChem 104A, UC, Berkeley


The problem of accounting for the true geometry of molecules and the
directionality of orbitals is handled using the concept of hybrid orbitals.
Hybrid orbitals are mixtures of atomic orbitals and are treated mathematically
as linear combinations of the appropriate s, p and d atomic orbitals.

Linear sp hybrid orbitals

A 2s orbital superimposed 1 1
on a 2px orbital 1  s  p The two resultant sp
2 2
hybrid orbitals that are
1 1 directed along the x-axis
2  s  p (in this case)
2 2
The 1/2 are normalization coefficients.

3
Chem 104A,
Example of the orthogonality of 1UC,
andBerkeley
2

1 1 1 1
1  s  p 2  s  p
2 2 2 2

 1 1  1 1 
      
1 2
2
s  p  
2  2
s   p  
2 

     2      2        2        2      
1 1 1 1
1 2 s s s p s p p p

1 1 1 1
     2 1  2 0  2 0  2 1
1 2

1 1
     2  2  0
1 2

Thus our hybrid sp orbitals are orthogonal to each other, as required.

Chem 104A, UC, Berkeley


Hybridization
Valence bond theory treatment of a linear molecule: the bonding in BeH2
BeH2 The promotion energy can
2s 2p be considered a part of the
Be energy required to form
hybrid orbitals.
Be*
sp 2p
Be* (sp)

2H
1s 1s
H Be H
The overlap of the hybrid orbitals on Be with the 1s orbitals on the H
atoms gives two Be-H (sp)-1s  bonds oriented 180° from each other.
This agrees with the VSEPR theory prediction.

4
Chem 104A, UC, Berkeley

p s
character character
Bonding 67% 33%
orbital

Chem 104A, UC, Berkeley

Valence bond theory treatment of a trigonal planar molecule: the bonding in BH3

2s 2p
B

B*

sp2 2p
B* (sp2)

1 1 1
1  s  p  p
y This gives three sp2 orbitals 3 6 x 2 y
that are oriented 120° 1 1 1
apart in the xy plane – be 2  s   px  p
3 6 2 y
x careful: the choice of axes
1 2
in this example determines 3  s  p
3 6 x
the set of coefficients.

5
Chem 104A, UC, Berkeley

The coefficients in front of each atomic wavefunction indicate the amount


of each atomic orbital that is used in the hybrid orbital. The sign indicates
the orientation (direction) of the atomic orbitals. Remember that you have
to use each atomic orbital completely (columns) and that each hybrid must
be normal (rows). Check this by summing the squares of the coefficients.
The signs in front
1 1 1 of the coefficients
1  s   px  p 1/3 + 1/6 + 1/2 = 1
So this hybrid is normal indicate the
3 6 2 y direction of the
hybrid:
1 1 1
2  s   px  p 1/3 + 1/6 + 1/2 = 1 1: -x, +y
3 6 2 y So this hybrid is normal
2: -x, -y

1 2 3: +x, 0y
3  s  p 1/3 + 4/6 = 1
3 6 x So this hybrid is normal y

1/3 + 1/3 + 1/3 = 1 1/6 + 1/6 + 4/6 = 1 1/2 + 1/2 = 1


x
So the entire s orbital So the entire px orbital So the entire py orbital
has been used has been used has been used

Chem 104A, UC, Berkeley

Valence bond theory treatment of a trigonal planar molecule: the bonding in BH3

sp2 2p
B*

3H
1s 1s 1s

H
H B
H
The overlap of the sp2 hybrid orbitals on B with the 1s orbitals on the H
atoms gives three B-H (sp2)-1s  bonds oriented 120° from each other.
This agrees with the VSEPR theory prediction.

6
Chem 104A, UC, Berkeley

p s
character character
Bonding 75% 25%
orbital

Chem 104A, UC, Berkeley

Valence bond theory treatment of a tetrahedral molecule: the bonding in CH4

2s 2p
C

C*
sp3
C* (sp3)

1 1 1 1
1  s  p  p  p
This gives four sp3 orbitals 4 4 x 4 y 4 z
that are oriented in a 1 1 1 1
H 2  s  p  p  p
tetrahedral fashion. 4 4 x 4 y 4 z
H C H 3 
1
s 
1
p 
1
p 
1
p
4 4 x 4 y 4 z
H 1 1 1 1
4  s  p  p  p
4 4 x 4 y 4 z

1
Chem 104A, UC, Berkeley

Valence bond theory treatment of a tetrahedral molecule: the bonding in CH4

2s 2p
C

C*
sp3
C* (sp3)

4H H
1s 1s 1s 1s
C H
H
H
The overlap of the sp3 hybrid orbitals on C with the 1s orbitals on the H
atoms gives four C-H (sp3)-1s  bonds oriented 109.47° from each
other. This provides the tetrahedral geometry predicted by VSEPR
theory.

2
Chem 104A, UC, Berkeley

Chem 104A, UC, Berkeley

1
Chem 104A, UC, Berkeley

Chem 104A, UC, Berkeley

Trigonal bipyramidal

2
Chem 104A, UC, Berkeley
Valence bond theory treatment of a trigonal bipyramidal molecule:
the bonding in PF5
3s 3p PF5 has a VSEPR theory AX5
P geometry so we need hybrid
3d orbitals suitable for bonds to
P* 5 atoms. ns and np
combinations can only
P* (sp3d) 3d provide four, so we need to
use nd orbitals (if they are
available).

3s 3pz 3py 3px 3dz2


sp3dz2

The appropriate mixture to form a trigonal bipyramidal arrangement


of hybrids involves all the ns and np orbitals as well as the ndz2
orbital.

Chem 104A, UC, Berkeley


Valence bond theory treatment of a trigonal bipyramidal molecule
The orbitals are treated in two different sets.

1 1 1 These coefficients are


1  s  p  p
3 6 x 2 y exactly the same as the
1 1 1 result for the trigonal
2  s   px  p planar molecules
3 6 2 y
because they are
1 2 derived from the same
3  s  p
3 6 x orbitals (sp2)

1 1 These coefficients are


4   pz  d similar to those for the sp
2 2 z2
hybrids because they are
1 1 formed from a combination
5   p  d
2 z 2 z2 of two orbitals (pd).

Remember that d orbitals are more diffuse than s or p orbitals so VBT


predicts that the bonds formed by hybrids involving d orbitals will be longer
than those formed by s and p hybrids.

3
Chem 104A, UC, Berkeley
Valence bond theory treatment of a trigonal bipyramidal molecule:
the bonding in PF5

P* (sp3d) 3d

F
2s 2p
F F
2s 2p 2s 2p
F
2s 2p
F
2s 2p
The overlap of the sp3d
hybrid orbitals on P with the 2p orbitals on the F
atoms gives five P-F (sp3d)-2p  bonds in two sets: the two axial bonds
along the z-axis (180° from each other) and three equatorial bonds in
the xy plane (120° from each other and 90° from each axial bond).
This means that the 5 bonds are not equivalent!

Chem 104A, UC, Berkeley

octahedral

4
Chem 104A, UC, Berkeley
Valence bond theory treatment of an octahedral molecule:
the bonding in SF6
3s 3p
S
3d
S*

S* (sp3d2) 3d

F F F F F F

3s 3pz 3py 3px 3dz2 3dx2-y2 sp3d2

The overlap of the sp3d2 hybrid orbitals on S with the 2p orbitals on the F
atoms gives six S-F (sp3d2)-2p  bonds 90° from each other that are
equivalent. You can figure out the normalization coefficients.

5
Chem 104A, UC, Berkeley
Valence bond theory treatment of bonding: a hypervalent molecule, ClF3
3s 3p F
Cl
3d
F Cl
Cl* F
There are five “objects” around
Cl* (sp3d) 3d
Cl so the geometry is trigonal
bipyramidal and the shape is
F F F given by AX3E2 (T-shaped).

The overlap of the sp3d hybrid orbitals on Cl with the 2p orbitals on the F
atoms gives three P-F (sp3d)-2p  bonds in two sets: the two axial bonds
along the z-axis (less than 180° from each other because of the
repulsion from the lone pairs) and the one equatorial bond halfway
between the other Cl bonds. Again, the bond lengths will not be the
same because there is more d contribution to the axial hybrid orbitals.

Chem 104A, UC, Berkeley

1
Chem 104A, UC, Berkeley

VBT does not adequately explain:

1. Excited state properties O O


2. Paramagnetism of oxygen: Lewis structure
presence of unpaired electrons

3. Bond in hypervalent molecules,


energy cost too high

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