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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Acryloyl Chloride and Acryloyl Isocyanate (CH_2=CHC(0)X, X = Cl, NCO): A HeI Photoelectron Spectroscopy and Theoretical Study
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Acryloyl Chloride and Acryloyl Isocyanate (CH_2=CHC(0)X, X = Cl, NCO): A HeI Photoelectron Spectroscopy and Theoretical Study

机译：丙烯酰氯和丙烯酰异氰酸酯（CH_2 = CHC（0）X，X = Cl，NCO）：HeI光电子能谱和理论研究

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摘要

Acryloyl isocyanate CH_2= CHC(0)NCO is quantitatively prepared by the metathesis reaction between CH_2=CHC(0)Cl and AgNCO. Also, jointly with acryloyl chloride, their molecular and electronic structures have been investigated by photoionization mass spectroscopy (PIMS), HeI photoelectron spectroscopy (PES), and theoretical calculations. CH_2=CHC(0)NCO was theoretically predicted to prefer the trans-cis (tc) conformation as the most stable conformer, with the C=0 bond trans to the C=C bond and cis to the NCO moiety. IR and Raman spectra also suggest the presence of the trans-cis (tc) conformation only. Calculations of the cationic-radical form were carried out in order to compare their properties with those of the neutral molecules. It is worthwhile mentioning that both compounds retain planar structures after ionization. After structural optimizations, a theoretical study involving the calculation of the ionization energies using orbital valence Green's functional (OVGF) was performed. The ionization energies of different bands in the photoelectron spectrum are in good agreement with the calculated values from the OVGF method. The first vertical ionization energies of CH_2=CHC(0)Cl and CH_2=CHC(0)NCO are determined to be 10.97 and 10.68 eV, respectively. The HOMOs correspond to the ionization of electrons mainly localized on the π_(C=C) or the π_(NCO) orbitals: {4a"(π_(C=C))}~(-1) and {5a"(π_(NCO))}~(-1), respectively.
机译：通过CH_2 = CHC（0）Cl与AgNCO之间的复分解反应定量制备丙烯酰基异氰酸酯CH_2 = CHC（0）NCO。另外，与丙烯酰氯一起，它们的分子和电子结构已经通过光电离质谱（PIMS），HEI光电子能谱（PES）和理论计算进行了研究。从理论上预测，CH_2 = CHC（0）NCO更喜欢反式顺式（tc）构象作为最稳定的构象异构体，其中C = 0的键反过来成为C = C键，顺式的则变为NCO部分。 IR和拉曼光谱也暗示仅反式（tc）构象的存在。为了比较阳离子自由基形式与中性分子的性质，进行了计算。值得一提的是，两种化合物在电离后均保留平面结构。经过结构优化后，进行了涉及使用轨道价格林函数（OVGF）计算电离能的理论研究。光电子能谱中不同能带的电离能与OVGF方法计算出的值非常吻合。 CH_2 = CHC（0）Cl和CH_2 = CHC（0）NCO的第一垂直电离能分别确定为10.97和10.68 eV。 HOMO对应于主要位于π_（C = C）或π_（NCO）轨道上的电子的电离：{4a“（π_（C = C））}〜（-1）和{5a”（π_（ NCO）}}〜（-1）。

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