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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.
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.
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.
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.
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'.
Orbitals Energies
ψA2' -3.4 eV
ψE',c ψE',d -13.2 eV
ψA1' -15.4 eV
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.