Towards New Chiroptical Transitions Based on Thought Experiments and Hypothesis

Abstract

We studied supramolecular chirality induced by circularly polarized light. Photoresponsive azopolymers form a helical intermolecular network. Furthermore, studies on photochemical materials using optical vortex light will also attract attention in the future. In contrast to circularly polarized light carrying spin angular momentum, an optical vortex with a spiral wave front and carrying orbital angular momentum may impart torque upon irradiated materials. In this review, we summarize a few examples, and then theoretically and computationally deduce the differences in spin angular momentum and orbital angular momentum depending on molecular orientation not on, but in, polymer films. UV-vis absorption and circular dichroism (CD) spectra are consequences of electric dipole transition and magnetic dipole transition, respectively. However, the basic effect of vortex light is postulated to originate from quadrupole transition. Therefore, we explored the simulated CD spectra of azo dyes with the aid of conventional density functional theory (DFT) calculations and preliminary theoretical discussions of the transition of CD. Either linearly or circularly polarized UV light causes the trans–cis photoisomerization of azo dyes, leading to anisotropic and/or helically organized methyl orange, respectively, which may be detectable by CD spectroscopy after some technical treatments. Our preliminary theoretical results may be useful for future experiments on the irradiation of UV light under vortex.