On the Dissociation of the Naphthalene Radical Cation: New iPEPICO and Tandem Mass Spectrometry Results

West, Brandi; Joblin, C.; Blanchet, Valérie; Bodi, Andras; Sztáray, Bálint; Mayer, Paul M.

doi:10.1021/jp3091705

Cited by 75 publications

(150 citation statements)

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“…On one hand, the two α-carbon atoms of the naphthalene molecular ion can directly establish a new bond to yield the bicyclic structure 7, the highest intermediate still in M. The dissociation of one C-C bond 7 → 12 connects M to branch D, to eventually yield the benzocyclobutadiene radical cation (F 2a ), as the minor structure for [M-C 2 H 2 ] +• . For this region of the PES profile, [12]. On the other hand, the lowest transition state in the energy profile that contributes to directly decompose M is TS 5−11 at 4.05 eV (Fig.…”

Section: Fig 3 Ub3lyp/6-31g(dp)-optimized Geometries Of Selected Imentioning

confidence: 92%

“…9 Different mass spectrometry techniques have been used to study the energetics of the decompositions of the radical cation of naphthalene ([C 10 H 8 ] +• , m/z 128) and to shed light on the products. [10][11][12] Both collision-induced • ] + , it is usually assumed to be a direct C-H bond dissociation, either from the α-or β-positions of 1 (F4a, F4b), with a critical energy E 0 ranging from 4.20 to 4.48 eV.…”

Section: Introductionmentioning

confidence: 99%

“…13 Similarly, ion [C 10 H 6 ] +• (F3a in Scheme 1) could be generated by H 2 loss from 1, 12-14 with a critical energy of 4.72 eV, 12 15 (F2a) and phenylacetylene 11 (F2b) cations, generated by multistep isomerizations (1 → → 12, 1 → → 10) followed by dissociations (Scheme 1). 13 Schroeder and co-workers have provided some experimental evidence in favor of F2a.…”

Section: Introductionmentioning

confidence: 99%

“…Unimolecular decompositions of the naphthalene molecular ion 1. 11,12 Multiple arrows represent multiple elementary steps. Dashed arrows show those steps for which no first-order saddle point transition state has been reported.…”

Section: Introductionmentioning

confidence: 99%

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A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

Solano

Mayer

2015

The Journal of Chemical Physics

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A theoretical study of the reaction of O ( 3 P) with an allyl radical C 3 H 5 J. Chem. Phys. 119, 8966 (2003) The fragmentation mechanisms of the naphthalene molecular ion to [M-+ were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)'s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)'s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0-18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Zand E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H 2 molecule in a two-step fragmentation. H• loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C 4 H 2 ) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%-100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M-C 2 H 2 ] +• structure is the phenylacetylene cation. C 2015 AIP Publishing LLC. [http://dx

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Section: Fig 3 Ub3lyp/6-31g(dp)-optimized Geometries Of Selected Imentioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

Solano

Mayer

2015

The Journal of Chemical Physics

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“…However, since the metastable peak broadening of the H-loss peak is negligible, the centre-ofgravity analysis of this band quantifies the individual contributions of the parent ion and the H-loss product. 36,37 The center of gravity of the parent and H-loss peaks is evaluated as:…”

Section: Breakdown Diagrammentioning

confidence: 99%

Dissociative ionisation of adamantane: a combined theoretical and experimental study

Candian

Bouwman

Hemberger

et al. 2018

Phys. Chem. Chem. Phys.

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aDiamond nanoparticles, or nanodiamonds, are intriguing carbon-based materials which, maybe surprisingly, are the most abundant constituent of presolar grains. While the spectroscopic properties of even quite large diamondoids have already been explored, little is known about their unimolecular fragmentation processes. In this paper we characterise the dissociative ionisation of adamantane (C 10 H 16 ) -the smallest member of the diamondoid family -utilising imaging Photoelectron Photoion Coincidence (iPEPICO) spectroscopy and Density Functional Theory (DFT) calculations. We have found adamantane to dissociatively photoionise via several parallel channels of which H, C 3 H 7 and C 4 H 8 losses are the most important ones. Calculations confirm the existence of a rate-limiting transition state for the multiple C-loss channels, which is located at 10.55 eV with respect to neutral adamantane. In addition, we found dissociation channels leading to small cationic hydrocarbons, which may be relevant in the interstellar medium.

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Dissociative Ionization and Thermal Decomposition of Cyclopentanone

Pastoors

Bodi

Hemberger

et al. 2017

Chemistry A European J

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Despite the growing use of renewable and sustainable biofuels in transportation, their combustion chemistry is poorly understood, limiting our efforts to reduce harmful emissions. Here we report on the (dissociative) ionization and the thermal decomposition mechanism of cyclopentanone, studied using imaging photoelectron photoion coincidence spectroscopy. The fragmentation of the ions is dominated by loss of CO, C2H4, and C2H5, leading to daughter ions at m/z 56 and 55. Exploring the C5H8O. + potential energy surface reveals hydrogen tunneling to play an important role in low‐energy decarbonylation and probably also in the ethene‐loss processes, yielding 1‐butene and methylketene cations, respectively. At higher energies, pathways without a reverse barrier open up to oxopropenyl and cyclopropanone cations by ethyl‐radical loss and a second ethene‐loss channel, respectively. A statistical Rice–Ramsperger–Kassel–Marcus model is employed to test the viability of this mechanism. The pyrolysis of cyclopentanone is studied at temperatures ranging from about 800 to 1100 K. Closed‐shell pyrolysis products, namely 1,3‐butadiene, ketene, propyne, allene, and ethene, are identified based on their photoion mass‐selected threshold photoelectron spectrum. Furthermore, reactive radical species such as allyl, propargyl, and methyl are found. A reaction mechanism is derived incorporating both stable and reactive species, which were not predicted in prior computational studies.

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On the Dissociation of the Naphthalene Radical Cation: New iPEPICO and Tandem Mass Spectrometry Results

Cited by 75 publications

References 28 publications

A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

Dissociative ionisation of adamantane: a combined theoretical and experimental study

Dissociative Ionization and Thermal Decomposition of Cyclopentanone

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