title: Novel coherent two-dimensional optical spectroscopy probes of chirality exchange and fluctuations in molecules.
abstract: We demonstrate how stochastic transitions between molecular configurations with opposite senses of chirality may be probed by 2D optical signals with specific pulse polarization configurations. The third-order optical response of molecular dimers (such as biphenyls) with dynamical axial chirality is calculated to order of k(2) in the wavevector of light. Spectroscopic signatures of equilibrium chirality fluctuations are predicted for three dynamical models (Ornstein-Uhlenbeck, two-state jump, and diffusion in double well) of the dihedral angle that controls the chirality.
authors: Institute of Physics, Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, Prague, 121 16, Czech Republic. sanda@karlov.mff.cuni.cz
authors: František
authors: F
authors: Šanda
authors: Shaul
authors: S
authors: Mukamel
mesh_terms: D001713:Biphenyl Compounds / Q000737:chemistry*; D019281:Dimerization; D056004:Molecular Dynamics Simulation; D013057:Spectrum Analysis / Q000379:methods*
chemical_list: D001713:Biphenyl Compounds; C010574:biphenyl