Unimolecular dissociation of aniline molecular ion: A theoretical study

The potential energy Surface (PES) for dissociation of aniline ion was determined using density functional theory molecular orbital calculations at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) level. On the basis of the PES obtained, kinetic analysis was performed by Rice-Ramsperger-Kassel-Marcus (RRKM) calculations. The RRKM dissociation rate constants agreed well with previous experimental data. The most favorable channel was formation of the cyclopentadiene ion by loss of HNC, occurring through consecutive ring opening and re-closure to a five-membered ring. Loss of H-center dot could compete with the HNC loss at high energy, which occurred by direct cleavage of an N-H bond or through ring expansion. (C) 2008 Elsevier B.V. All rights reserved.