Department of Chemistry, University of California, Berkeley, California 94720, USA.
Phys Chem Chem Phys. 2011 Oct 14;13(38):17378-83. doi: 10.1039/c1cp22211b. Epub 2011 Aug 31.
High resolution anion photodetachment spectra of the phenoxide and thiophenoxide anions were obtained with slow electron velocity-map imaging. The spectra show transitions to the X(2)B(1) neutral states of both species and to the Ã(2)B(2) state of the thiophenoxy radical. Comparison of the spectra with Franck-Condon simulations allows several gas-phase vibrations to be assigned. The adiabatic electron affinities are determined to be 2.2538(8) eV and 2.3542(6) eV for phenoxy and thiophenoxy, respectively. The term energy of the Ã(2)B(2) state of thiophenoxy is found to be 0.3719(9) eV, higher than the values reported in photodissociation experiments of thiophenol.
用慢电子速度映射成像技术获得了苯酚和苯硫酚阴离子的高分辨率阴离子光电子能谱。这些光谱显示了两种物质的 X(2)B(1)中性态以及苯硫氧基自由基的 Ã(2)B(2)态的跃迁。与 Franck-Condon 模拟的比较允许对几个气相振动进行分配。分别确定苯酚和苯硫酚的绝热电子亲和力为 2.2538(8) eV 和 2.3542(6) eV。发现苯硫氧基的 Ã(2)B(2)态的项能量为 0.3719(9) eV，高于苯硫酚光解实验中报道的值。
