Absorption anisotropy of cubic or randomly oriented chromophores in anisotropic solvents. Dispersion induced linear dichroism (DILD)

A new mechanism through which cubic or orientationally averaged solutes could gain absorption anisotropy (linear dichroism) in the presence of an anisotropic (oriented) solvent medium is proposed. Transitions of the unoriented species exhibit a dispersion induced linear dichroism (DILD) as a result of dispersive coupling to the transitions of the oriented system. The phenomenon depends on the nature of the angular distribution of solute molecules about a particular solvent species, being maximised for a cylindrical distribution around a polymer, but still yielding a measurable DILD for spherical distributions of the solute. It is also shown that the LD of non-cubic or oriented solutes in anisotropic media should be corrected for a significant DILD contribution.