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Walsh Cyclopropane Molecular Orbitals

Derivation of the Molecular Orbitals


Walsh considered cyclopropane as a combination of three methylene (CH2) units:

3 + 3 =

However, it should be obvious that the σ-type and π-type methylene orbitals cannot combine,
since they have different symmetries. We are left to make two separate sets of molecular orbitals
for cyclopropane.

Combinations of the methylene a1 orbitals

Group theoretical considerations tell us that those cyclopropane MOs derived


by combining the σ-type methylene MOs must belong to either the A1´ or E´
irreducible representations of the D3h point group.

The orbital of A1´ symmetry (which we will call ψA1´) is qualitatively


obvious; it is a totally symmetric combination of the three σ-type methylene
orbitals. The a1´ orbital has net bonding character.
Rigorous derivation of the a1´ MO.

The orbitals of E´ symmetry are not so obvious. Two of them are needed, and they will be
energetically degenerate. In order to qualitatively generate two e´ orbitals, pick one of the three
vertical planes of symmetry and construct combinations that are respectively symmetric (ψE´,a)
and antisymmetric (ψE´,b) to that plane. Notice that these orbitals have net antibonding
character.
symmetric antisymmetric
Rigorous derivation of the σ-type e´ MOs.

Combinations of the methylene b2 orbitals

The orbitals derived from the π-type methylene orbitals must belong to either
the A2´ or E´ irreducible representations of the D3h group.

Again, summing the three orbitals yields the more symmetric a2´ molecular
orbital, ψA2´. This time, the A-symmetric orbital has net antibonding
character.
Rigorous derivation of the a2´ MO.

Two orbitals of E´ symmetry are also required, and they will be energetically degenerate. In order
to qualitatively generate two e´ orbitals, we again pick one of the three vertical planes of
symmetry and construct combinations that are antisymmetric (ψE´,c) and symmetric (ψE´,d) to
that plane. Notice that these orbitals have net bonding character.

antisymmetric symmetric
Rigorous derivation of the π-type e´ MOs.

Background Walsh Cyclopropane home Orbital energy diagram

Copyright © 1997 by Daniel J. Berger. This work may be copied without limit if its use is to be
for non-profit educational purposes. Such copies may be by any method, present or future. The
author requests only that this statement accompany all such copies. All rights to publication for
profit are retained by the author.

Images generated with HyperChem Lite and ChemWindow Suite.


Walsh Cyclopropane Molecular Orbitals
Orbital Energy Diagram
Sketched orbitals Calculated orbitals

Molecular orbitals and energies are from Extended Hückel calculations.

It should be qualitatively apparent that the a1' MO (ψA1') is more bonding than the MOs ψE',c
and ψE',d; therefore we place ψA1' below the e' pair. And since the bonding combination of the
methylene a1 orbitals is more bonding than the bonding combination of the methylene b2
orbitals, we also expect the antibonding combinations ψE',a and ψE',b to be higher in energy than
the antibonding orbital ψA2'.

Extended Hückel calculations bear out this qualitative analysis.

Orbitals Energies

ψE',a ψE',b +6.8 eV

ψA2' -3.4 eV
ψE',c ψE',d -13.2 eV

ψA1' -15.4 eV

Derivation of the MOs Walsh Cyclopropane home Conclusions

Calculated orbitals

Copyright © 1997 by Daniel J. Berger. This work may be copied without limit if its use is to be for
non-profit educational purposes. Such copies may be by any method, present or future. The author
requests only that this statement accompany all such copies. All rights to publication for profit are
retained by the author.

Images generated with HyperChem Lite and ChemWindow Suite.