Hergenhahn Uwe, Rennie Emma E, Kugeler Oliver, Marburger Simon, Lischke Toralf, Powis Ivan, Garcia Gustavo
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany.
J Chem Phys. 2004 Mar 8;120(10):4553-6. doi: 10.1063/1.1651474.
The inner-shell photoionization of unoriented camphor molecules by circularly polarized light has been investigated from threshold to a photoelectron kinetic energy of approximately 65 eV. Photoelectron spectra of the carbonyl C 1s orbital, recorded at the magic angle of 54.7 degrees with respect to the light propagation direction, show an asymmetry of up to 6% on change of either the photon helicity or molecular enantiomer. These observations reveal a circular dichroism in the angle resolved emission with an asymmetry between forward and backward scattering (i.e., 0 degrees and 180 degrees to the light beam) which can exceed 12%. Since the initial state is an atomiclike spherically symmetric orbital, this strongly suggests that the asymmetry is caused by final-state effects dependent on the chiral geometry of the molecule. These findings are confirmed by electron multiple scattering calculations of the photoionization dynamics in the electric-dipole approximation.
我们研究了非定向樟脑分子在圆偏振光作用下的内壳层光电离过程,范围从阈值到光电子动能约为65电子伏特。在相对于光传播方向54.7度的魔角下记录的羰基C 1s轨道的光电子能谱显示,当光子螺旋度或分子对映体发生变化时,不对称性高达6%。这些观察结果揭示了角度分辨发射中的圆二色性,前向和后向散射(即相对于光束为0度和180度)之间的不对称性可超过12%。由于初始态是类原子的球对称轨道,这强烈表明不对称性是由依赖于分子手性几何结构的末态效应引起的。这些发现通过电偶极近似下光电离动力学的电子多重散射计算得到了证实。