Can we still measure circular dichroism with circular dichroism spectrometers: The dangers of anisotropic artifacts

Chiral materials with strong linear anisotropies are difficult to accurately characterize with circular dichroism (CD) because of artifactual contributions to their spectra from linear dichroism (LD) and birefringence (LB). Historically, researchers have used a second-order Taylor series expansion on the Mueller matrix to model the LDLB interaction effects on the spectra in conventional materials, but this approach may no longer be sufficient to account for the artifactual CD signals in emergent materials. In this work, we present an expression to model the measured CD using a third-order expansion, which introduces "pairwise interference" terms that, unlike the LDLB terms, cannot be averaged out of the signal. We find that the third-order pairwise interference terms can make noticeable contributions to the simulated CD spectra. Using numerical simulations of the measured CD across a broad range of linear and chiral anisotropy parameters, the LDLB interactions are most prominent in samples that have strong linear anisotropies (LD, LB) but negligible chiral anisotropies, where the measured CD strays from the chirality-induced CD by factors greater than 103 . Additionally, the pairwise interactions are most significant in systems with moderate-to-strong chiral and linear anisotropies, where the measured CD is inflated twofold, a figure that grows as linear anisotropies approach their maximum. In summary, media with moderate-to-strong linear anisotropy are in great danger of having their CD altered by these effects in subtle manners. This work highlights the significance of considering distortions in CD measurements through higher-order pairwise interference effects in highly anisotropic nanomaterials.