Institute of Physics, Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, Prague, 121 16, Czech Republic.
J Chem Phys. 2011 Nov 21;135(19):194201. doi: 10.1063/1.3658277.
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.
我们展示了如何通过具有特定脉冲偏振配置的二维光学信号来探测分子构型中具有相反手性的随机跃迁。我们计算了具有动态轴向手性的分子二聚体（如联苯）的三阶光学响应，其在光的波矢中达到 k(2)的阶数。我们预测了三种二面角动态模型（Ornstein-Uhlenbeck、两态跃迁和双势阱扩散）的平衡手性波动的光谱特征，该二面角控制着手性。
