Energy digram and optical transitions in naphthalene:

8 1
9
7 2

6 3
10
5 4
y
x

Naphthalene belongs to the point group D 2h . For simplicity, we can analyze it within D 2
group and choose appropriate subscripts later. When 10 p z ( orbitals are taken as
the basis set for a representation of this group, we obtain Γ . The character matrix is
also shown below. By custom, z axis is chosen parallel to p z orbitals.
D 2h E C 2 z C 2 y C 2 x i xy xz yz
Ag 1 1 1 1 1 1 1 1
B 1g 1 1 −1 −1 1 1 −1 −1
B 2g 1 −1 1 −1 1 −1 1 −1
B 3g 1 −1 −1 1 1 −1 −1 1
Au 1 1 1 1 −1 −1 −1 −1
B 1u 1 1 −1 −1 1 −1 1 1
B 2u 1 −1 1 −1 −1 1 −1 1
B 3u 1 −1 −1 1 −1 1 1 −1
Γ 10 0 −2 0 0 −10 0 2
That representation can be reduced into the irreducible ones for this point group:
Γ   2B 2g  3B 3g  2A u  3B 1u
Now we can construct symmetry adapted molecular  −orbitals. Projection operator for
each symmetry species, P  ∑ R   R ∗ O R , produces:
B 2g : P B 2g  1O E − 1O C 2 z  1O C 2 y − 1O C 2 x  1O i − 1O xy  1O xz − 1O yz .
If operating on p 1 , it results in P B 2g p 1  2p 1 − p 5 − p 8  p 4  , but obviously there should
be another function orthogonal to this one. Operation on p 2 , we get
P B 2g p 2  2p 2 − p 6 − p 7  p 3 . Thus we found two symmetry adapted functions for
B 2g . The same way for others. After normalizing we have:

1
 1
B 2g  1  2
p 1 − p 5 − p 8  p 4  H 11   H 12  
1
2  2
p 2 − p 6 − p 7  p 3  H 21   H 22   − 
1
B 3g  3  2
p 1 − p 4 − p 5  p 8    2
1
4  2
p 2 − p 3 − p 6  p 7   − 0
1
5  p 9 − p 10  2 0 −
2
1
Au 6  2
p 1 − p 4  p 5 − p 8   
1
7  2
p 2 − p 3  p 6 − p 7   −
1
B 1u  8  2
p 1  p 4  p 5  p 8    2
1
9  2
p 2  p 3  p 6  p 7    0
1
 10  p 9  p 10  2 0 
2

In the Huckel approximation, the matrix elements in Hamiltonian can be found using
 p i |H|p i  ;  p i |H|p j neihgbor   and  p i |H|p j nonneihgbor  0. For example
H 11   1 |H| 1  12 p 1 − p 5 − p 8  p 4 |H| 12 p 1 − p 5 − p 8  p 4  
 14  p 1 |H|p 1    p 5 |H|p 5    p 8 |H|p 8    p 4 |H|p 4   
The cross elements are all zeros here because neither p 1 , p 5 , p 8 or p 4 neighbor each
other. Other elements are calculated the same way:
H 12  H 21   1 |H| 2  14  p 1 − p 5 − p 8  p 4 |H|p 2 − p 6 − p 7  p 3  
 14  p 1 |H|p 2 − p 6 − p 7  p 3   −  p 5 |H|p 2 − p 6 − p 7  p 3   −  p 8 |H|p 2 − p 6 − p 7  p 3
  p 4 |H|p 2 − p 6 − p 7  p 3    14  p 1 |H|p 2    p 5 |H|p 6    p 8 |H|p 7    p 4 |H|p 3 
Now the secular equation is also reduced from 10x10 to two of 2x2 and two 3x3:
   12 5  1
2 1 1
B 2g : , eigenvectors: ↔ − 2
 2
 5
 − 1

  2 0
B 3g :  − 0 , eigenvectors: − 2 ↔  − ,
2 0 − 1
1 1
4
2  4
2 13
1 1
1
2
2 ↔ − 2
 2
 13
1

   12 5  1
2 1 1
Au : eigenvectors: ↔ − 2
 2
 5
 − 1

  2 0
B 1u :   0 , eigenvectors: − 2 ↔   ,
2 0  1

2
 − 14 2  1
4
2 13
1 1
1
2
2 ↔  2
 2
 13
1
After normalizing and substituting orbitals we get:

B3g(3) -2.303 3b3g 0.301(p1p4p5p8)  0.231(p2p3p6p7)0.461(p9p10)

(2)
Au -1.618 2au 0.263(p1p4p5p8)  0.425(p2p3p6p7)
(3)
B1u -1.3033b1u 0.400(p1p4p5p8)  0.174(p2p3p6p7)0.347(p9p10)
B3g(2) -1.000b3g 0.408(p2p3p6p7)0.408(p9p10)

B2g(2) -0.618b2g 0.425(p1p4p5p8)  0.263(p2p3p6p7)

Au(1) 0.618au 0.425(p1p4p5p8) + 0.263(p2p3p6p7)

B1u(2) 1.000b1u 0.408(p1p4p5p8)  0.408(p9p10)
B3g(1) 1.303b3g 0.400(p1p4p5p8) + 0.174(p2p3p6p7)0.347(p9p10)
B2g(1) 1.618b2g 0.263(p1p4p5p8) + 0.425(p2p3p6p7)
B1u(1) 2.303b1u 0.301(p1p4p5p8)  0.231(p2p3p6p7)0.461(p9p10)

3b3g -2.303 3b3g 0.301(p1p4p5p8)  0.231(p2p3p6p7)0.461(p9p10)

2au -1.618 2au 0.263(p1p4p5p8)  0.425(p2p3p6p7)
3b1u -1.3033b1u 0.400(p1p4p5p8)  0.174(p2p3p6p7)0.347(p9p10)
2b3g -1.000b3g 0.408(p2p3p6p7)0.408(p9p10)

2b2g -0.618b2g 0.425(p1p4p5p8)  0.263(p2p3p6p7)

1au 0.618au 0.425(p1p4p5p8) + 0.263(p2p3p6p7)

2b1u 1.000b1u 0.408(p1p4p5p8)  0.408(p9p10)
1b3g 1.303b3g 0.400(p1p4p5p8) + 0.174(p2p3p6p7)0.347(p9p10)
1b2g 1.618b2g 0.263(p1p4p5p8) + 0.425(p2p3p6p7)
1b1u 2.303b1u 0.301(p1p4p5p8)  0.231(p2p3p6p7)0.461(p9p10)

3
So, the ground state configuration of naphthalene is
1b 1u  2 1b 2g  2 1b 3g  2 2b 1u  2 1a u  2  A g
What about excitations?
Low energy singlet excited state configurations are:
B 2u :1b 1u  2 1b 2g  2 1b 3g  2 2b 1u  2 1a u 2b 2g with energy E  -0.618 - 0.618  -1.236
2 2 2 2
B 3u :1b 1u  1b 2g  1b 3g  2b 1u  1a u 2b 3g with energy E  -1.000 -0.618  -1.618
2 2 2 1 2
B 3u :1b 1u  1b 2g  1b 3g  2b 1u  1a u  2b 2g with energy E  0.618-(-0.618)  -1.618

B3u

B3u

B3u
B2u
B2u

B+3u

The two B 3u configurations have the same energy and higher than that of the B 2u but,
due to their interaction, they split into B 3u and B −3u . Calculation of these new energies is
more involved but can be qualitatively analysed as interaction between two transition
dipole moments oriented along x axis either with constructive or destructive
interference. The one with lower energy (dipoles are attracting each other) has to have
lower transition moment (dipole moments subtract each other). The higher energy
one, on the other hand, has much stronger transition. It happens that in naphthalene
B 3u state is lower in energy than B 2u thus warning that a simplification of the lowest
energy transition being that between HOMO and LUMO can fail (and often does).