In the present work, we use tunable synchrotron radiation to investigate experimentally and theoretically the dissociation of a chlorinated methane, the CHCl₃molecule, by exciting a chlorine 2p core electron into the LUMO and LUMO + 1 orbitals. The Auger electron energy distribution measured at the Cl 2p_3/2 → 10a₁ resonance shows narrow lines which energies correspond to the Cl^* → Cl⁺ atomic decay, a clear evidence that the Auger decay takes place after consummation of the dissociation, when the moieties were already far away from each other. Our experimental data are endorsed theoretically by a series of high-level ab initio quantum mechanical calculations. The excited states are calculated to be strongly repulsive in the Franck–Condon region (−dE/dy ∼ 0.15 a.u.) along the C–Cl bond direction.

在当前的工作中，我们使用可调谐同步辐射，通过将氯2 p核电子激发到LUMO和LUMO + 1轨道上，从理论上对氯化甲烷CHCl ₃分子的解离进行研究。在Cl 2p _3/2 →10a ₁共振下测得的俄歇电子能分布显示出窄线，其能量对应于Cl ^* →Cl ⁺原子衰变，这清楚地证明了俄歇衰变发生在解离完善后，各部分之间已经相距遥远。我们的实验数据在理论上得到了一系列高级从头算的认可量子力学计算。激发态被计算为在弗兰克-康登区域（-d强烈排斥ë / d ý沿C-Cl键方向〜0.15 AU）。