Lecture 31: H uckel Method

Julie H. Hwang November 26, 2007

Suggested Reading McQuarrie pg. 390-399

Introduction
H uckels molecular-orbital theory, or so-called H uckels rule, was rst introduced in organic chemistry to explain the stability of aromatic compounds. A simple version of H uckels rule states that for a cyclic compound, if there are (4n+2) electrons (n is zero or any positive integer) in the conjugated orbitals, the compound will possess aromaticity. Compounds with (4n) electrons were called anti-aromatic. H uckels rule in general explains the stability of conjugated orbitals. In organic chemistry, we explained this special stability using the resonance theory, but in this lecture, we will prove the H uckels rule using secular equation.

-electron approximation
In this lecture, we will calculate the stability of orbital of ethylene, C2 H4 . The following is the -bond framework of ethylene from McQuarrie Figure 10.19.

As we can see from the hybridization, one p orbital in each carbon did not participate in hybridization. If we assume that all the bonds in the -bond framework lies on the xy 1

plane of the cartesian coordinate system, the extra pz orbitals from the carbon atoms can form an extra bond that is perpendicular to the xy plane. We learned before that this is the bond between the two central carbons. This does not seem to be a complicated assumption. The point we are making here is that the unsaturation, or an additional -bonding comes from the p-orbitals that did not participate in the formation of the -bond framework. Because the -bond framework is the foundation for any molecular structures, we can view the -electrons as moving along the -bond framework. This approximation is called the -electron approximation .

Quantum Mechanical Formulation of bond

From the previous approximation, we can see that the -bond in ethylene comes from the linear combination of two pz orbitals. If we name two carbons as A and B, we can write the wavefunction as = c1 2pzA + c2 2pzB . Using the secular determinant, like we did for H+ 2 bonding, we can solve for the energy of the bonding. H11 S11 E H12 S12 E =0 H21 S21 E H22 S22 E We know from previous lectures that the Hij are integrals involving Hamiltonian operator of the system, and the Sij are the overlap integrals. Lets think of ways to evaluate each integral. Hii integrals Because two carbon atoms that participate in the bonding are equivalent, the values of H11 and H22 will be equivalent. This integral is equal to the energy of an electron in an isolated carbon 2p orbital. We will call this integral Coulomb integral . Although the name is same, this integral is dierent from the previous Coulomb integral we saw in He atom and H+ 2 molecule. For simplicity, we will let this integral equal to , in other words, H11 = H22 = . Hij integrals We can also say that the values of H12 and H21 are the same, because two carbon atoms are equivalent. This integral, as weve seen earlier, is the lowering energy by allowing the electron to occupy both 2p orbitals from A and B. We will call this integral Resonance integral . For simplicity, we will also set this integral equal to . H12 = H21 = .

Sij integrals As the name suggests, the overlap integral value can be obtained from evaluating the overlap of two pz orbitals from carbons A and B. If i = j , the integral will equal to 1, and if i = j , the integral will equal to 0, because there is no overlap between pz orbitals from dierent carbons. Sii = 1 Sij = 0 (i = j ).

Using these simplications and deductions, we can simplify the determinant and solve for E . E =0 E = E We know that is the energy of the electron in an isolated 2p orbital, so we can use this as the reference point for the energy diagram. We do not know the Hamiltonian of the system, but the value has been experimentally determined to be negative. So we draw the energy diagram for the system.

We can see from the picture that the energy of two electrons are equal to E = 2 + 2 . The energies, + and correspond to the energy of bonding orbital (HOMO) and anti-bonding orbital (LUMO), respectively. Solving for the coecients, we get 1 |c1 | = |c2 | = 2 To designate bonding and antibonding, we simply change the sign of c2 and we obtain the wavefunctions of the bond. 1 b = 2pzA + 2 1 = 2pzA 2 3 1 2pzB 2 1 2pzB 2

QM Formulation of Conjugated bonds

The next example we will take a look at is conjugated butadiene. As we know from organic chemistry, there are two butadiene congurations, but for the sake of calculation, we will treat this as a linear molecule (resembling trans conguration more). In the case of butadiene, we are combining 4 orbitals, so we will end up with 4 4 determinant. The formulation is as follows.
4

i =
j =1

cij 2pzj H13 S13 E H23 S23 E H33 S33 E H43 S43 E H14 S14 E H24 S24 E H34 S34 E H44 S44 E

H11 S11 E H21 S21 E H31 S31 E H41 S41 E

H12 S12 E H22 S22 E H32 S32 E H42 S42 E

=0

Using the same approximations from ethylene, the determinant can be simplied using and formulation. Added approximation for butadiene is that the p orbitals will not interact if they are not adjacent. Mathematical formulation of this statement is Hij = 0 i |i j | > 1 Then the determinant becomes as follows. E 0 0 E 0 0 E 0 0 E Solving the determinant, we obtain 4 energy values, E = 1.618, 0.618 Calculating the energy of the electrons, we obtain the total -electronic energy. E = 2( + 1.618 ) + 2( + 0.618 ) = 4 + 4.472 At this point, lets make an assumption. If the 4 2p-orbital overlap was not conjugated (2 bonds at each end), the total energy would be equivalent to the energy of 2 ethylene, which is 4 + 4 . The energy dierence between conjugated and nonconjugated butadiene is E = (4 + 4.472 ) (4 + 4 ) = 0.472 We know that the value is negative, which means that the conjugation lowers the energy of the system. This energy dierence is called the delocalization energy , because the extra stabilization, or lowering of the energy, comes from the electrons being delocalized over the conjugated -network. 4

=0

QM Formulation of Benzene Ring

The last example for today is a benzene ring. Using similar technique that we used for ethylene and butadiene, we can obtain the following secular determinant. Be aware of the ring arrangement, i.e. carbon 1 and 6 are next to each other. E 0 0 0 E 0 0 0 0 E 0 0 0 0 E 0 0 0 0 E 0 0 0 E

=0

Solving this,we obtain 6 energies. Note that some of the energies are repeated! (degeneracy) E = 2, , The total electron energy is given as E = 2( + 2 ) + 4( + ) = 6 + 8 and the delocalization energy, using the same assumption as we did in butadiene calculation, is Edeloc = (6 + 8 ) (6 + 6 ) = 2 This is even lower than the delocalization energy of butadiene! From todays calculation, we can conclude that conjugation stabilizes the system, and aromatic systems are more stable than the linear conjugation of orbitals. 5

Summary
H uckels method is eective in calculating the energy of conjugated hydrocarbons. By limiting our focus to the network, we can calculate dierent MO energy levels and also obtain degeneracy. From the calculation, we can gure out the bond order and delocalization energy as well. Even though we did not calculate the exact energy, H uckels method gave us an idea as how to combine atomic orbitals and calculate molecular orbitals. H uckels idea formed a basis in todays quantum calculation, and this method was further modied by Roald Homann and today it is called the extended H uckel method. (Actually this extended H uckel method, or also known as WoodwardHomann rules, are the rules that we learned in organic chemistry on aromaticity and anti-aromaticity.)