Isomerization and dissociation of the acetonitrile molecular cation

Joong Chul Choe

doi:10.1016/j.ijms.2004.03.003

Isomerization and dissociation of the acetonitrile molecular cation

Joong Chul Choe

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

Abstract

The unimolecular dissociation of the acetonitrile molecular cation (CH ₃CN·⁺) has been investigated using mass-analyzed ion kinetic energy spectrometry. Kinetic energy release distribution was obtained for the H loss. Density functional theory calculations have been performed to investigate isomerization and dissociation of CH ₃CN·⁺. The potential energy surface (PES) for the H loss has been constructed from the calculations at the UB3LYP/6-311++G(3df,3pd) level. The RRKM model calculations based on the obtained PES predict that CH₃CN·⁺ interconverts to CH₂CNH· ⁺ and CH₂NCH·⁺ followed by dissociation to a cyclic C₂H₂N⁺ via a cyclic C ₂H₃N·⁺ intermediate near the threshold. The present and previous experimental data for the dissociations of C ₂H₃N·⁺ isomers are interpreted with the theoretical results.

Original language	English
Pages (from-to)	15-23
Number of pages	9
Journal	International Journal of Mass Spectrometry
Volume	235
Issue number	1
DOIs	https://doi.org/10.1016/j.ijms.2004.03.003
State	Published - Jun 2004

Keywords

Acetonitrile ion
DFT calculation
Isomerization
Unimolecular dissociation

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title = "Isomerization and dissociation of the acetonitrile molecular cation",

abstract = "The unimolecular dissociation of the acetonitrile molecular cation (CH 3CN·+) has been investigated using mass-analyzed ion kinetic energy spectrometry. Kinetic energy release distribution was obtained for the H loss. Density functional theory calculations have been performed to investigate isomerization and dissociation of CH 3CN·+. The potential energy surface (PES) for the H loss has been constructed from the calculations at the UB3LYP/6-311++G(3df,3pd) level. The RRKM model calculations based on the obtained PES predict that CH3CN·+ interconverts to CH2CNH· + and CH2NCH·+ followed by dissociation to a cyclic C2H2N+ via a cyclic C 2H3N·+ intermediate near the threshold. The present and previous experimental data for the dissociations of C 2H3N·+ isomers are interpreted with the theoretical results.",

keywords = "Acetonitrile ion, DFT calculation, Isomerization, Unimolecular dissociation",

author = "Choe, {Joong Chul}",

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T1 - Isomerization and dissociation of the acetonitrile molecular cation

AU - Choe, Joong Chul

PY - 2004/6

Y1 - 2004/6

N2 - The unimolecular dissociation of the acetonitrile molecular cation (CH 3CN·+) has been investigated using mass-analyzed ion kinetic energy spectrometry. Kinetic energy release distribution was obtained for the H loss. Density functional theory calculations have been performed to investigate isomerization and dissociation of CH 3CN·+. The potential energy surface (PES) for the H loss has been constructed from the calculations at the UB3LYP/6-311++G(3df,3pd) level. The RRKM model calculations based on the obtained PES predict that CH3CN·+ interconverts to CH2CNH· + and CH2NCH·+ followed by dissociation to a cyclic C2H2N+ via a cyclic C 2H3N·+ intermediate near the threshold. The present and previous experimental data for the dissociations of C 2H3N·+ isomers are interpreted with the theoretical results.

AB - The unimolecular dissociation of the acetonitrile molecular cation (CH 3CN·+) has been investigated using mass-analyzed ion kinetic energy spectrometry. Kinetic energy release distribution was obtained for the H loss. Density functional theory calculations have been performed to investigate isomerization and dissociation of CH 3CN·+. The potential energy surface (PES) for the H loss has been constructed from the calculations at the UB3LYP/6-311++G(3df,3pd) level. The RRKM model calculations based on the obtained PES predict that CH3CN·+ interconverts to CH2CNH· + and CH2NCH·+ followed by dissociation to a cyclic C2H2N+ via a cyclic C 2H3N·+ intermediate near the threshold. The present and previous experimental data for the dissociations of C 2H3N·+ isomers are interpreted with the theoretical results.

KW - Acetonitrile ion

KW - DFT calculation

KW - Isomerization

KW - Unimolecular dissociation

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U2 - 10.1016/j.ijms.2004.03.003

DO - 10.1016/j.ijms.2004.03.003

M3 - Article

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VL - 235

SP - 15

EP - 23

JO - International Journal of Mass Spectrometry

JF - International Journal of Mass Spectrometry

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ER -

Isomerization and dissociation of the acetonitrile molecular cation

Abstract

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