Photoelectron spectra of halides. Part II. High-resolution spectra of the boron trihalides
Photoelectron spectra of halides. Part II. High-resolution spectra of the boron trihalides
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DOI：
10.1039/j19710001551
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发表时间：
1971
期刊：
影响因子：
--
通讯作者：
P. J. Bassett;D. R. Lloyd
中科院分区：
文献类型：
--
作者：
P. J. Bassett;D. R. Lloyd
用圆柱形偏转分析仪和HeI共振辐射测量了三氟化硼、三氯化物、三溴化硼和三碘化硼的光电子能谱。垂直电离势，在大多数情况下，绝热电离势也列在表中。在BF3和BCl3谱中观察到振动精细结构，BBr3和BCl3的一些谱带出现分裂，归因于自旋-轨道耦合。根据能带分裂、精细结构和与计算结果的关联对光谱进行了解释；BF3的指认与最近的高斯基分子轨道计算很好地一致。从π轨道的能量推断，分子的π稳定能遵循顺序BF3>；BCl3>；(Br3∼Bl3)，但有证据表明这仍然与π-电子离域的相反顺序一致。
The photoelectron spectra of boron trifluoride, trichloride, tribromide, and tri-iodide have been obtained by use of a cylindrical deflection analyser instrument and HeI resonance radiation. Vertical ionization potentials, and in most cases adiabatic ionization potential also, are tabulated. Vibrational fine structure is observed in the BF3 and BCl3 spectra, and some of the bands of BBr3 and Bl3 show splittings ascribed to spin–orbit coupling. The spectra are interpreted on the basis of band splittings, fine structure, and correlation with the results of calculations; the BF3 assignment is in good agreement with recent Gaussian basis molecular orbital calculations. From the energies of the π orbitals it is deduced that the molecular π stablisation energy follows the sequence BF3 > BCl3 > (BBr3∼ Bl3), but evidence is presented that this is still consistent with the opposite sequence of π-electron delocalisation.