5.

04, Principles of Inorganic Chemistry II

MIT Department of Chemistry
Lecture 9: N-Dimensional Cyclic Systems

Polynomial Derivation

3
2
1

N-1

N-2
where N is the total number of orbitals

The Hückel determinant is given by,

x 1
1 x 1
1 x

1



-E
DN (x) =


=0 where x =







1

x 1
1 x

From a Laplace expansion one finds,

DN(x) = xDn-1(x) – DN-2(x)

where

D1(x) = x

x 1
D2 (x) = = x2
1
1 x

with these defined, the polynomial form of DN(x) for any value of N can be
obtained,

D3(x) = xD2(x) - D1(x) = x(x2-1) – x = x(x2–2)

D4(x) = xD3(x) – D2(x) = x2(x 2-2) – (x2-1)

and so on

5.04, Principles of Inorganic Chemistry II Lecture 9

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 The expansion of DN(x) has as its solution,

2

x = 2cos j (j = 0,1,2,3...N  1)
N

and substituting for x,

2

E =  + 2 cos j (j = 0,1,2,3...N  1)
N

Standing Wave Derivation

An alternative approach to solving this problem is to express the wave

function directly in an angular coordinate, 

m+1 m
m-1

N-1
N-2

For a standing wave of  about the perimeter of a circle of circumference c,

c
 j = sin



The solution to the wave function must be single valued  a single solution
must be obtained for  at every 2n
…

c c
 = sin ( + 2
) = sin 

 

c c c c c
= sin   cos 2
+ sin 2
 cos  = sin 
    

must go to 1 must go to 0

c
if 2
= 2
j (j = 0, 1, 2... N  1)

condition for an integral
c
number of ’s about the  =j
circumference of a circle

5.04, Principles of Inorganic Chemistry II Lecture 9

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Thus the amplitude of j at atom m is,

2
m
 j(m) = sin j (j = 0,1,2,...N  1)
N

Within the context of the LCAO method, j may be rewritten as a linear

combination in m with coefficients Cjm… thus the amplitude of  at m is
equivalent to the coefficient of m in the LCAO expansion,

j =
C 
jm m
m=1

2m
where cjm = sin j (j = 0,1,2...N  1)
N

The energy of each MO, j, may be determined from a solution of

Schrödinger’s equation:

H j = E j  j
H  Ej j = 0
N

H  Ej
c jm m
 =0
m

The energy of the m orbital is obtained by left–multiplying by m,

m H  E j
c 
jm m =0
m

but the Hückel condition is imposed; thus only terms retained are those
involving m, m+1, and m-1. Expanding,

1  0
   
c  Hm
cjmE j m m + cj(m+1) m Hm+1
cj(m+1)E j m m+1 
 jm m   
 
+ cj(m
1) m Hm
1
cj(m
1)E j m m
1  = 0
 
 0

5.04, Principles of Inorganic Chemistry II Lecture 9

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Evaluating the appropriate integrals,

( )
 Cjm
CjmE j +  Cj(m+1) + Cj(m
1) = 0

( )
 Cjm +  Cj(m+1) + Cj(m
1) = CjmE j

Substituting for Cjm,

2
m  2
(m + 1) 2
(m  1)  2
m

 sin j +  sin j + sin j
= E j sin j
N  N N  N

2
m
Dividing by sin j,
N

 2
(m + 1) 2
(m  1) 
 sin j + sin j

 N N 

+ = Ej
2
m
sin j
N

Making the simplifying

E j =  +

(
 sin (m + 1) + sin (m
1) )

sin m

 sin m  cos  + sin  cos m + sin m  cos 
sin  cos m 

E j =  + 

 sin m

Ej =
+ 2cos

2

E j =  + 2 cos j (j = 0,1,2...N  1)

5.04, Principles of Inorganic Chemistry II Lecture 9

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Let’s look at the simplest cyclic system, N = 3

2

1

3 2

N = 3... E j =  + 2 cos j, j = 0,1,2
N

E0 =  + 2
2

E1 =  + 2 cos = 
3

4

E2 =  + 2 cos = 
3

Continuing with our approach (LCAO) and using Ej to solve for the
eigenfunction, we find…

 N
± for N even
j =
eij m for j = 0, ± 1, ± 2...  2

m ± (N  1)
for N odd
 2
 1  1
where  j ~
2i
( )
 j

j and  j ~  j + 
j = cos j
2
( )
Using the general expression for
j, the eigenfunctions are:

2
4

i(0) i(0)
0 = e i(0)0
1 + e 3
2 + e 3
3

2
4

i(1) i(1)
+1 = ei(1)01 + e 3
2 + e 3
3

2
4

i(1) i(1)
1 = ei(1)01 + e 3
2 + e 3
3

Obtaining real components, and normalizing,

1
0 = 1 + 2 + 3  0 =
3

(
1 + 2 + 3 )
1
+1 + 
1 = 21
2
3  1 =
6

(2 1
2
3 )

1
+1

1 = 2
3  2 =
2
( 2
3 )

5.04, Principles of Inorganic Chemistry II Lecture 9

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Summarizing on a MO diagram (
= 0)
1

-2
2 3
-1
2

E/
0
6

1
6

2
0
1

5.04, Principles of Inorganic Chemistry II Lecture 9

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