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首页> 外文期刊>Physical chemistry chemical physics: PCCP >Electron attachment and intramolecular electron transfer in unsaturated chloroderivatives
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Electron attachment and intramolecular electron transfer in unsaturated chloroderivatives

机译：不饱和氯衍生物中的电子附着和分子内电子转移

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摘要

The electron transmission (ET) and dissociative electron attachment (DEA) spectra of chloroalkyl ethene and ethyne derivatives are reported. B3LYP/6-31G* calculations are employed to evaluate the virtual orbital energies for the optimised geometries of the neutral states of these molecules and other related pi-systems. The calculated pi* MO energies correlate linearly with the energies of electron attachment to the pi* LUMO measured in the ET spectra with a correlation coefficient of 0.993. The vertical attachment energies supplied by B3LYP/6-311+G** calculations, where the basis set includes diffuse functions, are often in significant disagreement with experiment, describing the singly occupied MO of the lowest-lying anion state as a diffuse sigma* MO rather than a valence pi* MO. The relative Cl- anion currents measured in the DEA spectra of the present molecular systems are compared to those previously found in benzene analogues. The Cl- yield reflects the efficiency of intramolecular electron transfer from the pi-system (where the extra electron is first trapped) to the remote chlorine atom. Replacement of a carbon atom with a silicon atom in the intermediate saturated alkyl chain causes a notable increase of the Cl- current, ascribed to the lower energy of the empty sigma*(Si-C) MOs and consequent greater ability to promote through-bond coupling between the pi* and sigma*(C-Cl) MOs. Comparison between the corresponding benzene, ethene and ethyne derivatives reveals that the Cl- current is also significantly influenced by the nature of the pi-functional group, in agreement with the inverse dependence on energy of the lifetime of the temporary pi* anion state. [References: 55]
机译：报道了氯烷基乙烯和乙炔衍生物的电子传输（ET）和离解电子附着（DEA）光谱。 B3LYP / 6-31G *计算用于评估虚拟轨道能量，以优化这些分子和其他相关pi系统的中性态几何形状。计算出的pi * MO能量与在ET光谱中测得的电子附着到pi * LUMO的能量线性相关，相关系数为0.993。由B3LYP / 6-311 + G **计算提供的垂直附着能，其中基集包括扩散函数，通常与实验有很大不同，将最低阴离子状态的单占据MO描述为扩散sigma *。 MO，而不是价pi * MO。将在本分子系统的DEA光谱中测得的相对阴离子电流与先前在苯类似物中发现的相对阴离子电流进行比较。 Cl收率反映了分子内电子从pi系统（首先捕获了多余的电子）转移到远端氯原子的效率。中间饱和烷基链中的硅原子取代碳原子会导致Cl电流显着增加，这归因于空sigma *（Si-C）MOs的能量较低，因此具有更大的促进键合能力pi *和sigma *（C-Cl）MO之间的耦合。相应的苯，乙烯和乙炔衍生物之间的比较表明，Cl电流也受到pi官能团性质的显着影响，这与对pi暂时性阴离子状态的寿命的能量负相关。 [参考：55]

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