Photoelectron Spectroscopic Investigation of the Electronic Structure of Nitromethane and Nitrobenzene
Photoelectron Spectroscopic Investigation of the Electronic Structure of Nitromethane and Nitrobenzene
复制标题
硝基甲烷和硝基苯电子结构的光电子能谱研究
DOI：
10.1063/1.1678346
复制
发表时间：
1972
影响因子：
4.4
通讯作者：
J. Rabalais
中科院分区：
文献类型：
--
作者：
J. Rabalais
通过高分辨率 HeI 光电子能谱和 INDO 型量子化学计算研究了硝基甲烷和硝基苯的电子结构。 CH3NO2 和 CD3NO2 的光谱显示出 6 个低于 21 eV 的电离带。向基态和第一激发离子态的跃迁具有广泛的振动结构，已被确定为对称的 NO2 弯曲模式。 C6H5NO2 和 C6D5NO2 的光谱包含至少 10 个低于 21 eV 的电离带，仅在向基离子态跃迁时具有解析的振动结构。硝基甲烷最松散的 MO 已被确定为 5a1 NO2-σ 键合轨道，硝基苯的最松散的 MO 被确定为 b1 环-π 轨道。非键合 a2 π 轨道已分配给这些各自分子中的第二和第四电离带。使用此处发现的 MO 排序，硝基甲烷的 198 mμ 吸收带被分配给 π*(2b1)← σ(5a1) 跃迁，而硝基苯的长波长带是...
The electronic structure of nitromethane and nitrobenzene has been studied by high‐resolution HeI photoelectron spectroscopy and quantum chemical calculations of the INDO type. The spectra of CH3NO2 and CD3NO2 exhibit six ionization bands below 21 eV. The transitions to the ground and first excited ionic states have extensive vibrational structure which has been identified as the symmetric NO2 bending mode. The spectra of C6H5NO2 and C6D5NO2 contain at least 10 ionization bands below 21 eV with resolved vibrational structure only in the transition to the ground ionic state. The most loosely bound MO of nitromethane has been identified as the 5a1 NO2–σ bonding orbital, and that of nitrobenzene as the b1 ring‐π orbital. The nonbonding a2 π orbital has been assigned to the second and fourth ionization bands in these respective molecules. Using the MO ordering found here, the 198 mμ absorption band of nitromethane is assigned to the π*(2b1)← σ(5a1) transition and the long wavelength bands of nitrobenzene are ...