PFI-ZEKE光电子能谱学研究碘代二乙炔自由基阳离子的自旋轨道耦合和振转结构
Spin-orbit coupling and rovibrational structure in the iododiacetylene radical cation by PFI-ZEKE photoelectron spectroscopy
摘要：
用脉冲场电离零动能（PFI-ZEKE）光电子能谱学记录了碘代二乙炔（HC $_4$ I）中$\textrm{X}^{+}\,{}^{2}Π\leftarrow \textrm{X}\,{}^{1}Σ^{+}$光电离跃迁的光电子能谱，并对转动结构进行了部分分辨。HC $_4$ I的第一绝热电离能和HC $_4$ I $^+$的X $^{+}\,{}^{2}Π$态的自旋轨道分裂分别确定为$E^{\textrm{ad}}_{\textrm{I}}/(hc) = 74470.7(2)$ cm $^{-1}$和$Δ\tildeν_{\textrm{so}} = 1916.7(4)$ cm $^{-1}$。观察到HC $_4$ I $^+$阳离子的X $^{+}\,{}^{2}Π$电子基态的几个振动能级。在一个简单的三态电荷转移模型，没有可调参数，允许HC $_4$ I $^+$的电子结构和自旋-轨道耦合的定性描述和HC $_4$ I电离后的键长变化的领域中的实验数据进行了讨论。
英文摘要：
The photoelectron spectrum of the $\textrm{X}^{+}\,{}^{2}Π\leftarrow \textrm{X}\,{}^{1}Σ^{+}$ photoionising transition in iododiacetylene, HC$_4$I, has been recorded using pulsed-field-ionisation zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy with partial resolution of the rotational structure. The first adiabatic ionisation energy of HC$_4$I and the spin-orbit splitting of the X$^{+}\,{}^{2}Π$ state of HC$_4$I$^+$ are determined as $E^{\textrm{ad}}_{\textrm{I}}/(hc) = 74470.7(2)$ cm$^{-1}$ and $Δ\tildeν_{\textrm{so}} = 1916.7(4)$ cm$^{-1}$, respectively. Several vibrational levels of the X$^{+}\,{}^{2}Π$ electronic ground state of the HC$_4$I$^+$ cation have been observed. The experimental data are discussed in the realm of a simple three-state charge-transfer model without adjustable parameters which allows for a qualitative description of the electronic structure and spin-orbit coupling in HC$_4$I$^+$ and of the change in bond lengths upon ionisation of HC$_4$I.
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