ja5b01763_si_001.pdf (43.09 MB)
Hückel Theory and Optical Activity
journal contribution
posted on 2015-04-22, 00:00 authored by Veronica
L. Murphy, Bart KahrOptical rotations and rotatory strengths
are calculated for achiral,
conjugated hydrocarbons with the aim of determining to what extent
the sum-over-π → π* rotatory strengths are sufficient
to account for nonresonant optical activity. The separability of σ
and π electrons might provide a short cut to the interpretation
of chiroptical structure–property relations in some cases.
It is shown that by restricting the analyses to planar, C2v-symmetric π-systems
and their one electron HOMO–LUMO excitations, an intuitive
understanding of the vexing property of optical activity is forthcoming
for the following reasons: Hückel wave functions are simply
calculated, and in some cases, they can even be approximated by inspection
of structure. Wave functions of planar molecules can be multiplied
with one another graphically or, in the mind’s eye, to yield
transition electric and magnetic moments. The gyration tensors have
just one independent component. Transition dipole moments are orthogonal
to one another. And, the most optically active directions are found
at their bisectors. Throughout, emphasis is on the evaluation of long
wavelength optical rotation, consistent with quantum chemical computation,
using simple models that are part of the fabric of organic chemistry
pedagogy.
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gyration tensorsinterpretationHOMOfabricanalyseshydrocarbonquantum chemical computationrotatory strengthsHuemphasisevaluation2vexcitationorthogonalwavelengthmoleculeTransitionchiropticalachiralunderstandingmomentbisectorextentOptical ActivityOptical rotationstransitionπ electronswave functionsaimseparabilitycomponentchemistry pedagogynonresonantmodelinspection
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