Anisotropic circular dichroism of jet-cooled chiral molecules

Abstract

Anisotropic circular dichroism (CD) refers to the CD of oriented molecules, which varies with the direction of light propagation toward the molecules. Thus, anisotropic CD spectroscopy has been used to investigate the orientations of molecules in anisotropic media such as liquid crystals and thin films. However, it is unclear whether anisotropic CD results from isolated chromophores or their intermolecular interactions with other atoms or molecules that form anisotropically aligned structures. Herein, anisotropic CD of isolated chiral molecules was observed for the first time. The resonant two-photon ionization CD spectra of jet-cooled pseudoephedrine and styrene oxide indicated a difference between the CD values of the P/R and Q branches of the origin bands of the S₀–S₁ transition. This difference may have resulted from the anisotropic CD phenomena of these molecules, which are oriented via photoselection. Although jet-cooled molecules may have nearly random orientations, those excited to the P/R or Q branch become oriented because the transition probability to these branches depends on the molecular orientation relative to the direction of light propagation. These results demonstrate that the CD spectra of cold, isolated molecules, such as those in an interstellar medium, may exhibit anisotropic CD values.