Journal Article10.1039/B304083F
Electron attachment and intramolecular electron transfer in unsaturated chloroderivatives
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TL;DR: The electron transmission and dissociative electron attachment (DEA) spectra of chloroalkyl ethene and ethyne derivatives are reported in this paper, where the virtual orbital energies for the optimised geometries of the neutral states of these molecules and other related π-systems are evaluated.
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Abstract: 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 π-systems. The calculated π* MO energies correlate linearly with the energies of electron attachment to the π* 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 σ* MO rather than a valence π* 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 π-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 σ*Si–C MOs and consequent greater ability to promote through-bond coupling between the π* and σ*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 π-functional group, in agreement with the inverse dependence on energy of the lifetime of the temporary π* anion state.
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