Branching ratios in the dissociative photoionization of iodomethane by photoelectron photoion coincidence

Bödi, András; Hafliðason, Arnar; Kvaran, Ágúst

doi:10.1039/d2cp03339a

Cited by 3 publications

(3 citation statements)

References 74 publications

(113 reference statements)

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“…24 A recent work on CH 3 I shed detailed light on the non-statistical competition between C-I and C-H bond breaking in the cation. 25 The observed pattern is similar to that observed in CH 3 Cl + where an excited state is responsible for a portion of the Cl loss pathway. 26 Indeed, OVGF energies for the ion states show that there is an excited state at 11.5 eV and three in close proximity between 11.9 and 7 Cl loss was shown to also dissociate in a non-statistical process from its second excited state, in which the chlorine atom is weakly bound to the ring.…”

Section: Pcfsupporting

confidence: 75%

“…Such non‐statistical halogen‐loss processes have also been observed in the relatively large Sn (CH 3 ) 3 Cl + cation 23 as well as in halogenated ethylene cations 24 . A recent work on CH 3 I shed detailed light on the non‐statistical competition between C–I and C–H bond breaking in the cation 25 . The observed pattern is similar to that observed in CH 3 Cl + where an excited state is responsible for a portion of the Cl loss pathway 26 .…”

Section: Resultsmentioning

confidence: 85%

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What a difference a chlorine makes: The remarkable unimolecular ion chemistry of phenyl formate and phenyl chloroformate

Lowe,

Cardona,

Salas

et al. 2024

J Mass Spectrom

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Imaging photoelectron photoion coincidence (iPEPICO) spectroscopy and tandem mass spectrometry were employed to explore the ionisation and dissociative ionisation of phenyl formate (PF) and phenyl chloroformate (PCF). The threshold photoelectron spectra of both compounds are featureless and lack a definitive origin transition, owing to the internal rotation of the formate functional group relative to the benzene ring, active upon ionisation. CBS‐QB3 calculations yield ionisation energies of 8.88 and 9.03 eV for PF and PCF, respectively. Ionised PF dissociates by the loss of CO via a transition state composed of a phenoxy cation and HCO moieties. The dissociation of PCF ions involves the competing losses of CO (m/z 128/130), Cl (m/z 121) and CO2 (m/z 112/114), with Cl loss also shown to occur from the second excited state in a non‐statistical process. The primary CO‐ and Cl‐loss fragment ions undergo sequential reactions leading to fragment ions at m/z 98 and 77. The mass‐analysed ion kinetic energy (MIKE) spectrum of PCF+ showed that the loss of CO2 occurs with a large reverse energy barrier, which is consistent with the computationally derived minimum energy reaction pathway.

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Section: Pcfsupporting

confidence: 75%

Section: Resultsmentioning

confidence: 85%

What a difference a chlorine makes: The remarkable unimolecular ion chemistry of phenyl formate and phenyl chloroformate

Lowe,

Cardona,

Salas

et al. 2024

J Mass Spectrom

Self Cite

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“…2c and 3c for (CH 2 I + , e) show a structureless continuum. The respective maximum eKE corresponds directly to a binding energy equal to the reported appearance threshold recently reported by Bodi et al 60 at ∼12.6 eV, while slightly below the value measured by Eland and coworkers (∼12.74 eV). 28 The H-atom elimination seems therefore to be open from both the upper part of the Ã state and from the B̃ manifold of states.…”

Section: Resultssupporting

confidence: 47%

Evidencing an elusive conical intersection in the dissociative photoionization of methyl iodide

González-Vázquez,

García,

Chicharro

et al. 2024

Chem. Sci.

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State-selective dissociative double ionization of CH3I and CH2I2 via I 4d core-hole states studied by multi-electron–ion coincidence spectroscopy

Fushitani,

Hikosaka,

Tashiro

et al. 2024

The Journal of Chemical Physics

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The dissociative double ionization of CH3I and CH2I2 irradiated with extreme ultraviolet light at hv = 100 eV is investigated by multi-electron–ion coincidence spectroscopy using a magnetic bottle type electron spectrometer. The spin–orbit state-resolved Auger electron spectra for the I 4d core-hole states, (I 4d3/2)−1 and (I 4d5/2)−1, provide clear identifications of electronic states of CH3I2+ and CH2I22+. The dominant ion species produced after the double ionization correlate with the Auger electron energy, showing that different fragmentation pathways are open depending on the electronic states populated by the Auger decay. Theoretical calculations are performed to understand the fragmentation from the doubly charged states and the observed spin–orbit specificity in the Auger decay.

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Branching ratios in the dissociative photoionization of iodomethane by photoelectron photoion coincidence

Abstract: After valence photoionization, iodomethane yields ten fragment ions by even more dissociation pathways, thanks to sequential paths sharing a fragment ion as well as the plethora of electronic states available...

Cited by 3 publications

References 74 publications

What a difference a chlorine makes: The remarkable unimolecular ion chemistry of phenyl formate and phenyl chloroformate

What a difference a chlorine makes: The remarkable unimolecular ion chemistry of phenyl formate and phenyl chloroformate

Evidencing an elusive conical intersection in the dissociative photoionization of methyl iodide

State-selective dissociative double ionization of CH3I and CH2I2 via I 4d core-hole states studied by multi-electron–ion coincidence spectroscopy

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