Hckels MO treatment of Benzene

Outlines

electron energy, MO coefficients Delocalization Energy Electrone Density Bond order

Hckel Theory:

An approximate theory that gives us a very quick picture of the MO energy diagram and MOs of molecules without doing a lot of work
Basic Assumptions: Atomic orbitals contributing to the -bonding in a planar molecule are treated independently

The Coulomb integrals for all the carbon atoms are assumed to be identical.
All resonance integrals between directly-bonded atoms are assumed to be the same; whilst those between atoms that are not directly bonded are neglected. All overlap integrals representing the overlap of atomic orbitals centred on different atoms are neglected
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 electron energy

Benzene Atomic orbitals 1, ..., 6.

We denote an MO with the symbol , and write it as a linear combination of AOs whose coefficients cr have to be determined:

Consider the energy of this MO Expanding the sum, we get

 electron energy

The first-derivative w.r.t cr is equal to zero

The cr which satisfy the above are given by the matrix equation

Written in matrix form we have we will assume that the overlap matrix is simply the identity matrix: We also set the off-diagonal elements between nearest-neighbour orbitals to be , and all others to be zero

 electron energy

HMO secular equation is

MO coefficients

For coefficients of corresponding AOs, we have The normalization condition Shows that all the coefficients in the jth MO have the same absolute value. Hence

Delocalization Energy

HMO theory can explain delocalization energy. The corresponding VB term is resonance energy. Given six -electrons, which doubly occupy the three lowest energy levels, the total energy is:

The energy of the occupied ethylene HMO

benzene has three isolated double bonds thus electron energy would be three time of ethylene ie

Delocalization Energy

benzene is more stable by 36 kcal/mol

Hckel theory predicts a similar stabilization of other cyclic conjugated systems with 4N+2 electrons. This energetic stabilization explains in part why benzene is so unreactive as compared to other unsaturated hydrocarbons.

Electrone Density

From HMO normalization condition it is natural to say that an electron in the MO of being in the vicinity of the rth carbon atom has the probability |cri|2

total -electron charge qr in the region of carbon-atom r is defined as

where the sum is over the it MOs. qr is often called the -electron density"; this name is misleading, since qr is neither a charge density (which has dimensions of charge/ volume) nor a probability density (which has dimensions of 1/volume). Rather, qr is a pure number that gives the approximate number of electrons in the vicinity of carbon atom r

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Bond order

Coulson defined the -electron (or mobile) bond order prs for the bond between bonded atoms r and s as When the coefficients are all real

Applying this formula to the 1-2 bond in benzene

Bond order

Addition of the electrons' single bond gives the total bond order

For benzene each carbon-carbon bond order is found to be 5/3 = 1.667

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