Ab initio molecular dynamics simulation study of dissociative electron attachment to C6H5(CH2)nCl (n = 0, 1, 2, 3, 4)

• CCl bond cleavage is faster in dissociative electron attachment to the 1-chloroalkyl benzene with a longer alkyl chain.
• Variance of the CCl bond cleavage time is in line with the dissociation thresholds of 1-chloroalkyl benzene anions.
• Electron transfer π* → σ* is the common feature of dissociative electron attachments to 1-chloroalkyl benzenes.

The CCl bond cleavages induced by electron attachment to 1-chloroalkyl benzenes [C6H5(CH2)nCl, n = 0, 1, 2, 3, 4] are investigated with ab initio molecular dynamics simulations. The fragment Cl− is generated and the CCl bond cleavage time decreases with the increasing length of the alkyl chain. In the dissociative electron attachment processes, the incoming electron is initially captured to the local π* virtual orbital of the phenyl group and then transfers to the anti-bond σ* orbital of the remote CCl moiety; the variation of the CCl bond cleavage times shows a similar trend of the dissociation thresholds of C6H5(CH2)nCl + e− → C6H5(CH2)n + Cl−.

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