A new pulsed four-wave mixing technique for the detection and
real-time measurement of circular dichroism
(CD) in liquid samples is demonstrated. The technique is based on
the formation and detection of transient thermal
gratings formed by the interference of two laser beams whose
polarizations are controlled and modulated using a
photoelastic modulator. Through an internal heterodyne process,
coherent thermal gratings interfere to greatly enhance
a weak circular dichroism signal. By measuring the ratio of the
difference of scattered laser light from two different
polarizations, ΔS, to the average amount of scattered
light, S
ave, one can determine the value of
Δε/ε for the compound
under investigation. Samples of chiral camphorquinone are used to
demonstrate the technique in the ultraviolet
region of the spectrum. These studies of camphorquinone, which has
a value of Δε/ε ≈ 10-3 at 266 nm,
produce
values of ΔS/S
ave which are orders
of magnitude larger than Δε/ε and which approach 2 (the
mathematical limit for
ΔS/S
ave). Possible extensions
of the technique for measuring CD in very small sample volumes and
monitoring
time-dependence are discussed.