Abstract:
The method of dissociative electron attachment (DEA) spectroscopy was used to study the attachment of electrons to 1-chloronaphthalene molecules. It has been established that the dominant channel for the decay of molecular ions is the formation of Cl$^-$ ions in three resonances at 0.7, 1.5, and 3.0 eV. Ions [M–H]$^-$ and [M–Cl]$^-$ are observed at energies from 3.5 to 8.5 eV and have two to three orders of magnitude lower formation cross sections. Long-lived molecular ions were not registered. Calculations in the DFT CAM B3LYP/6-311+G(d,p) approximation predict the presence of six stable anionic structures in which the chlorine anion is coordinated to the neutral residue via noncovalent H–Cl$^-$–H bonds. The electron affinity of the most stable of these structures coincides with the experimentally measured value $EA_a$ = 0.2771 $\pm$ 0.003 eV. These results agree with the previously obtained data on the DEA of molecules of bromine-substituted biphenyls, naphthalenes, and anthracenes and confirm the existence of anionic structures with non-covalent H–Hal–H bonds. Such non-covalent anion structures should be extremely reactive, which makes them promising for the synthesis of self-assembling hydrocarbon nanomembranes.
Keywords:attachment of electrons to molecules, electron affinity, potential surface, DFT calculations.
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