Abstract
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{radical dot} could compete with the HNC loss at high energy, which occurred by direct cleavage of an N-H bond or through ring expansion.
Original language | English |
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Pages (from-to) | 25-31 |
Number of pages | 7 |
Journal | International Journal of Mass Spectrometry |
Volume | 279 |
Issue number | 1 |
DOIs | |
State | Published - 1 Jan 2009 |
Keywords
- DFT calculation
- Ring contraction
- Ring expansion
- RRKM calculation