Vacuum-Ultraviolet Absorption Spectrum of 3-Methoxyacrylonitrile.
Vacuum-Ultraviolet Absorption Spectrum of 3-Methoxyacrylonitrile.
复制标题
3-甲氧基丙烯腈的真空紫外吸收光谱。
DOI：
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发表时间：
2020
影响因子：
2.9
通讯作者：
M. Briant
中科院分区：
文献类型：
--
作者：
A. Röder;N. de Oliveira;F. Grollau;J. Mestdagh;M. Gaveau;M. Briant
用同步辐射傅里叶变换光谱仪测量了3-甲氧基丙烯腈（3 MAN）在5.27 ~ 12.59 eV之间的高分辨吸收光谱。这与绝对吸收截面尺度有关。在DFT-MRCI/aug-cc-pVTZ理论水平上的补充计算证明了3 MAN的E和Z几何异构体的前19个态的垂直跃迁能和振子强度。与实验吸收光谱的比较揭示了3 MAN，一个双官能分子，与丙烯腈和甲基乙烯基醚，其中只有一个官能团存在的相似性和差异。在丙烯腈中，观察到几个广泛的价跃迁电离极限。它们可能与腈基诱导的扩展π系统有关，但也可能涉及接近电离极限的σσ* 跃迁。在甲基乙烯基醚，里德堡系列收敛到电离极限是缺席。这归因于甲基旋转60°导致的中性和阳离子几何形状的差异。
The high-resolution absorption spectrum of 3-methoxyacrylonitrile (3MAN) was measured between 5.27 and 12.59 eV using a synchrotron-based Fourier-transform spectrometer. It was related to an absolute absorption cross-section scale. Complementary calculations at the DFT-MRCI/aug-cc-pVTZ level of theory document the vertical transition energies and oscillator strengths toward the first 19 states of both the E and Z geometrical isomers of 3MAN. Comparisons with the experimental absorption spectrum reveal the similarities and differences between 3MAN, a bifunctional molecule, with acrylonitrile and methylvinylether, where only one functional group is present. As in acrylonitrile, several broad valence transitions were observed up to the ionization limit. They are likely associated with the extended π-system induced by the nitrile group but might also involve σσ* transitions close to the ionization limit. As in methylvinylether, Rydberg series converging to the ionization limit are absent. This is attributed to a difference in neutral and cationic geometry due to a 60° rotation of the methyl group.
DOI：
10.1002/wcms.1394
发表时间：
2018-10
期刊：
Wiley Interdisciplinary Reviews: Computational Molecular Science
影响因子：
--
作者：
C. Marian;Adrian Heil;M. Kleinschmidt
通讯作者：
C. Marian;Adrian Heil;M. Kleinschmidt