Departments of Chemistry and Physics, University of Virginia, Charlottesville, Virginia 22904-4319, USA.
J Chem Phys. 2018 Sep 7;149(9):094201. doi: 10.1063/1.5045052.
Pulse flip angles are calculated for three-wave mixing, three-state cycles of chiral molecules to produce optimized free induction decay amplitudes proportional to the enantiomeric excess of a sample and to produce optimized degrees of state-specific enantiomeric separation. The calculations account for the spatial degeneracy of the levels involved and the resulting inhomogeneous distribution of transition dipole moments. Cycles of transitions that include R followed by Q followed by P branch transitions display only modest reductions of the calculated optimal signals compared to those calculated if every M component was optimally polarized. Transition cycles P-Q-R are only slightly worse, while the Q-Q-Q cycles are much worse, increasingly so, as the rotational total quantum number is increased.
针对手性分子的三波混频、三态循环，计算脉冲翻转角，以产生与样品对映过量成正比的优化自由感应衰减幅度，并产生优化的状态特异性对映体分离程度。该计算考虑了涉及的能级的空间简并性以及跃迁偶极矩的不均匀分布。与每个 M 分量都被最佳极化相比，包括 R 后紧接着 Q 后紧接着 P 支跃迁的循环跃迁的计算最佳信号仅略有降低。P-Q-R 跃迁循环仅略差，而 Q-Q-Q 循环则差得多，随着转动总量子数的增加，情况变得越来越糟。
