Trend in the Electron Affinities of Fluorophenyl Radicals ·C 6 H 5-x F x (1 ≤ x ≤ 4)
Trend in the Electron Affinities of Fluorophenyl Radicals ·C 6 H 5-x F x (1 ≤ x ≤ 4)
复制标题
氟苯基自由基·C 6 H 5-x F x (1 ≤ x ≤ 4) 的电子亲和力变化趋势
DOI：
10.1021/acs.jpca.3c04327
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Jarrold, Caroline Chick
中科院分区：
文献类型：
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作者：
McGee, Conor J.;McGinnis, Kristen Rose;Jarrold, Caroline Chick
利用C6 H6-xFx（1 ≤x≤ 4）氟苯前体生成的氟代苯阴离子的光电子能谱，测定了一系列·C6 H5-xFx（1 ≤ x ≤ 4）氟苯基自由基的电子亲合势.光谱显示出0.4eV/x的EA的近线性增量增加。的光谱表现出振动未解决的和广泛的分离过渡的阴离子和中性自由基物种的分子结构的显着差异一致。这些物种的实验EA和宽光谱与密度泛函理论计算是一致的。虽然阴离子脱离跃迁都涉及非键合轨道中的电子，但中性和阴离子之间的结构差异部分是由于过量电荷所在的C中心上的孤对电子与相邻F原子之间的排斥。C6 H5-xFx-（2 ≤x≤ 4）光谱在较低的结合能下显示出一些特征，这些特征似乎是由于离子源中形成的结构异构体所致。
The electron affinities (EAs) of a series of ·C6H5–xFx(1 ≤x≤ 4) fluorophenyl radicals are determined from the photoelectron spectra of their associated fluorophenide anions generated from C6H6–xFx(1 ≤x≤ 4) fluorobenzene precursors. The spectra show a near-linear incremental increase in EA of 0.4 eV/x. The spectra exhibit vibrationally unresolved and broad detachment transitions consistent with significant differences in the molecular structures of the anion and neutral radical species. The experimental EAs and broad spectra are consistent with density functional theory calculations on these species. While the anion detachment transitions all involve an electron in a non-bonding orbital, the differences in structure between the neutral and anion are in part due to repulsion between the lone pair on the C-center on which the excess charge is localized and neighboring F atoms. The C6H5–xFx–(2 ≤x≤ 4) spectra show features at lower binding energy that appear to be due to constitutional isomers formed in the ion source.