Ionized limonene and related isomeric compounds have been examined by collisional activation at both gaseous and solid targets. The gas-phase collision-induced dissociation (CID) experiments were performed as a function of collision energy and scattering angle and the surface-induced dissociation (SID) experiments as a function of collision energy, in order to vary systematically the internal energy deposited in the molecular ion. The virtual absence of retro-Diels–Alder (RDA) fragmentation upon conventional CID, as compared to its importance in the electron impact (EI) mass spectrum, the subject of a study by Boyd and coworkers, was confirmed. However, as the ion internal energy was increased by raising the collision energy or the scattering angle, RDA fragmentation was observed and it became a dominant mode of fragmentation for SID at collision energies in the range of 25–50 eV. The energy deposited into the colliding ion in the SID technique is compared with that deposited upon CID in the eV and keV energy ranges and upon EI. The order obtained is: SID > EI > low-energy, multiple-collision CID > high-energy, single-collision CID > low-energy, single-collision CID. The distribution of energies in SID is narrower than in the other techniques. High internal energies are accessible by increasing the scattering angle in CID; however, this is accompanied by an increase in the width of the internal energy distribution, and it is therefore not possible to channel fragmentation predominantly into RDA by this method. It is concluded that RDA fragmentation of limonene is a high-energy process and that this is the explanation for its behavior. Isomerization, occurring through 1,3-hydrogen migrations of the molecular ions of limonene, isolimonene, terpinolene and α-terpinene, was investigated and long-lived molecular ions of the first three compounds were found to maintain distinct structures.
Energetics of Retro-Diels-Alder Fragmentation in Limonene as Characterized by Surface-Induced Dissociation, and Energy- and Angle-Resolved Mass Spectrometry
VINCENTI, Marco;
1988-01-01
Abstract
Ionized limonene and related isomeric compounds have been examined by collisional activation at both gaseous and solid targets. The gas-phase collision-induced dissociation (CID) experiments were performed as a function of collision energy and scattering angle and the surface-induced dissociation (SID) experiments as a function of collision energy, in order to vary systematically the internal energy deposited in the molecular ion. The virtual absence of retro-Diels–Alder (RDA) fragmentation upon conventional CID, as compared to its importance in the electron impact (EI) mass spectrum, the subject of a study by Boyd and coworkers, was confirmed. However, as the ion internal energy was increased by raising the collision energy or the scattering angle, RDA fragmentation was observed and it became a dominant mode of fragmentation for SID at collision energies in the range of 25–50 eV. The energy deposited into the colliding ion in the SID technique is compared with that deposited upon CID in the eV and keV energy ranges and upon EI. The order obtained is: SID > EI > low-energy, multiple-collision CID > high-energy, single-collision CID > low-energy, single-collision CID. The distribution of energies in SID is narrower than in the other techniques. High internal energies are accessible by increasing the scattering angle in CID; however, this is accompanied by an increase in the width of the internal energy distribution, and it is therefore not possible to channel fragmentation predominantly into RDA by this method. It is concluded that RDA fragmentation of limonene is a high-energy process and that this is the explanation for its behavior. Isomerization, occurring through 1,3-hydrogen migrations of the molecular ions of limonene, isolimonene, terpinolene and α-terpinene, was investigated and long-lived molecular ions of the first three compounds were found to maintain distinct structures.
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