5.

04, Principles of Inorganic Chemistry II

MIT Department of Chemistry
Lecture 8: Hückel Theory 2 (Eigenvalues)

The energies (eigenvalues) may be determined using the Hückel approximation.

1
 A1g =
6
(
1 +
2 +
3 +
4 +
5 +
6 )

( )

E  A1g = A1g H  A1gd =  A1g | H |  A1g

1 1
=
6
( + 
1 2 )
+ 3 + 4 + 5 + 6 | H |
6

( + 
1 2 + 3 + 4 + 5 + 6 )
1

= (H11 + H12 + H13 + H14 + H15 + H16 + H21 + H22 + H23 + H24 + H25 + H26
6

     

+ H3i (i = 1  6) + H4i(i = 1  6) + H5i(i = 1  6) + H6i(i = 1  6) )

+2 +2 +2 +2
1
( )
E  A1g =
6
(6)(
+ 2) =
+ 2

The energy of the LCAO, B2g…

( )
E B2g = B2g | H | B2g

1 1
=
6
(

1 2 )
+ 3
4 + 5
6 | H |
6

(

1 2 + 3
4 + 5
6 )
1

= (H11
H12 + H13
H14 + H15
H16

6

    (-2)

+ H2i(i = 1
6) + H3i + H4i + H5i + H6i )

-2 -2 -2 -2 -2

1
( )
E B2g =
6
(6)(
2) = 
2

5.04, Principles of Inorganic Chemistry II Lecture 8

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The energies of the remaining LCAO’s are:

( ) = E( ) =  + 
E Ea
1g Eb
1g

( ) = E( ) = 

E Ea
2u Eb
2u

Note the energies of the E orbitals are degenerate. Constructing the energy
level diagram, we set  = 0 and  as the energy parameter (a negative
quantity, so an MO whose energy is positive in units of  has an absolute
energy that is negative),

-2 B2g

-1 E2u
E/

1 E1g 6
electrons

2 A2u

The energy of benzene based on the Hückel approximation is

Etotal = 2(2) + 4() = 8

What is the delocalization energy (i.e.
resonance energy)?

To determine this, we consider cyclohexatriene… the cyclic with 3 localized

bonds. In other terms, the product of three condensed
molecules. For

ethylene,

1
2

5.04, Principles of Inorganic Chemistry II Lecture 8

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Following the procedures outlined above, we find,

1
1 (A) = (
1 +
2 ) 
2

1
2 (B) = (1
2 ) 
2

1 1 1
E(1 ) =
2
( 1 )
+ 2 | H |
2

( 1 + 2 ) =
2
(2 + 2) = 

1 1
1
E(2 ) =
2
( 1 )

2 | H |
2
( 1
2 ) =
2
(2
2) =


The above was determined in the C2 point group… correlating to D2h…

A in C2
B1u in D2h and B in C2
B2g in D2h :

-1 B2g
E/

1 B1u

The Hückel energy of ethylene is,

Etotal = 2() = 2

Therefore, the energy of cyclohexatriene is 3(2) = 6)… thus the resonance

energy is:

Eres(C6H6) = 8 - 6 = 2
 
Etotal Etotal
benzene cyclohexatriene

5.04, Principles of Inorganic Chemistry II Lecture 8

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The bond order is given by,
coefficients of a given bond

B.O. =
n c ce i j
i,j

e- occupancy

Consider the B.O. between the C1 and C2 carbons of benzene

 1  1 
1

[ ]

1 (A 2u ) = 2

 6  6
 =
3

 a   2  1  1

(E ) = 2

=
 3 1g 

 12 
 12  3
 b  1 1
2 2
()

4 (E1g ) = 0
 = 0

1 B.O = 2/3 (p
bond order)

6 2

5 3

5.04, Principles of Inorganic Chemistry II Lecture 8

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