Table-Top X-ray Spectroscopy of Benzene Radical Cation,The Journal of Physical Chemistry A

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Table-Top X-ray Spectroscopy of Benzene Radical Cation
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-10-27 , DOI: 10.1021/acs.jpca.0c08736
Michael Epshtein _{1,

2} , Valeriu Scutelnic ₁ , Zheyue Yang ₁ , Tian Xue ₁ , Marta L. Vidal ₃ , Anna I. Krylov ₄ , Sonia Coriani ₃ , Stephen R. Leone _{1,

2,

5}

Affiliation

Ultrafast table-top X-ray spectroscopy at the carbon K-edge is used to measure the X-ray spectral features of benzene radical cations (Bz⁺). The ground state of the cation is prepared selectively by two-photon ionization of neutral benzene, and the X-ray spectra are probed at early times after the ionization by transient absorption using X-rays produced by high harmonic generation (HHG). Bz⁺ is well-known to undergo Jahn–Teller distortion, leading to a lower symmetry and splitting of the π orbitals. Comparison of the X-ray absorption spectra of the neutral and the cation reveals a splitting of the two degenerate π* orbitals as well as an appearance of a new peak due to excitation to the partially occupied π-subshell. The π* orbital splitting of the cation, elucidated on the basis of high-level calculations in a companion theoretical paper [Vidal et al. J. Phys. Chem. A.http://dx.doi.org/10.1021/acs.jpca.0c08732], is discovered to be due to both the symmetry distortion and even more dominant spin coupling of the unpaired electron in the partially vacant π orbital (from ionization) with the unpaired electrons resulting from the transition from the 1s_C core orbital to the fully vacant π* orbitals.

中文翻译：

苯自由基阳离子的台式X射线光谱

碳K边缘的超快台式X射线光谱学用于测量苯自由基阳离子（Bz ⁺）的X射线光谱特征。阳离子的基态是通过中性苯的双光子电离选择性地制备的，并且在电离后的早期通过使用高谐波产生（HHG）产生的X射线通过瞬态吸收探测X射线光谱。Bz ⁺众所周知，Jahn-Teller失真会导致对称性降低和π轨道分裂。比较中性离子和阳离子的X射线吸收光谱，发现两个简并的π*轨道分裂，并且由于激发了部分占据的π-子壳而出现了一个新的峰。阳离子的π*轨道分裂，是在高层理论的基础上，在伴随的理论论文中阐明的[Vidal et al。J.物理化学 A. http://dx.doi.org/10.1021/acs.jpca.0c08732]被发现是由于部分空的π轨道（由于电离）中不成对电子的对称畸变和更显着的自旋耦合所致。）以及从1s _C跃迁产生的不成对电子核心轨道到完全空闲的π*轨道。

更新日期：2020-11-19

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